BLOCK 2

Chemistry of Air,
Water and Soil
UNIT 5 : ATMOSPHERIC CHEMISTRY

Structure
5.0 Introduction
5.1 Objectives
5.2 Origin of Atmosphere
5.3 Composition of Atmosphere
5.4 Structure of Atmosphere
5.5 Atmospheric stability
5.5.1 Atmospheric Lapse rate
5.5.2 Types of Lapse Rates
5.5.3 Lapse rates and Atmospheric Stability
5.5.4 Importance of Understanding Atmospheric Stability

5.6 Chemical and Photochemical Reactions of Atmosphere

5.6.1 Photochemistry of the Atmosphere

5.7 Distribution of Species in Atmosphere

5.7.1 Ions in the Atmosphere
5.7.2 Free Radicals in the Atmosphere

5.8 Reactions of Atmospheric Oxygen

5.9 Reactions of Atmospheric Ozone
5.10 Reactions of Nitrogen Oxides
5.11 Particles in the Atmosphere
5.11.1 Charecteristics of Particulates
5.11.2 Chemical Reactions of Atmospheric Particles
5.11.3 Aerosols
5.11.4 Black Carbon
5.11.5 Effects of Particulate Matter on Human Health

5.12 Let Us Sum Up

5.13 Key Words
5.14 References and Suggested Further Readings

5.0 INTRODUCTION

IMPORTANCE OF ATMOSPHERE
Atmosphere, the gaseous envelope of the earth, nurtures life on earth and protects
it from the harsh environment of the outer space. It serves as a source of oxygen
for the sustenance of life on earth and carbon dioxide for plant’s photosynthesis,
provides nitrogen which is consumed by nitrogen fixing bacteria in producing
nitrogen-based molecules, an essential component of life molecules. As a basis of
the hydrologic cycle, atmosphere provides a medium for the movement of water. The
atmosphere plays an important role in absorbing cosmic rays from outer space and
thus protects life from their adverse effects. By absorbing electromagnetic radiation
below wavelength 300 nm, the atmosphere filters out damaging ultraviolet rays
from the sun. Thus, atmosphere plays a significant role in stabilizing the Earth’s

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Chemistry of Air, temperature, by reabsorbing infrared radiation given off by earth and remitting the
Water and Soil absorbed solar energy back into space.

5.1 OBJECTIVES
After Studying this unit, you will be able to
• define atmosphere and describe its origin,
• classify atmosphere into various regions,
• describe the composition of atmosphere and its variation with height, latitude
and season,
• explain the process and types of atmospheric reactions
• understand the distribution of chemical species in the atmosphere
• describe the ozone layer depletion and its impact on biosphere

5.2 ORIGIN OF ATMOSPHERE

Origin and development of the atmosphere can be correlated to the origin of Earth.
Evolution of the atmosphere can be subdivided into three stages.

Stage I
Earth is believed to have formed about 4.5 billion years ago from a protoplanetary
gas-dust cloud. Hydrogen and helium were the basic gaseous components of
the cloud. Dust particles most likely contained metals and condensates of water,
ammonia, methane and mixtures of formaldehyde, methylacetylene, acetonitrile
and other compounds present in interstellar space. Due to gradual gravitational
contraction of the gas dust cloud, as well as the action of radioactive decay of
radionuclides, gravitational attraction of the simultaneously formed moon and other
processes, the cloud became heated, resulting in its partial melting. The formation
of the earth was an exothermic process. The large amounts of gases and vapours
possessing high kinetic energy so released got scattered into cosmic space. Thus,
a dense atmosphere so formed, about 3.5 x 109 years ago, contained hydrogen,
water, ammonia, methane,noble gases and some sulphur compounds as its main
components. At the initial stages, atmosphere was devoid of oxygen and thus was
reducing in nature.

At the same time, a massive condensation of water vapours paved the way for
gradual formation of the hydrosphere. This phenomenon affected the evolution
of the atmosphere, by dissolving carbon dioxide in liquid water which followed
the formation of the sedimentary rocks. On account of their low atomic masses,
hydrogen and helium escaped into space and the atmosphere became rich in
nitrogen.

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Stage II Atmospheric
The second stage of evolution initiated at around 3.5x109 years ago lasted at about Chemistry
2 x 109 years ago. During this period, volcanic eruptions resulted in the formation
of large quantities of magma, saturated with dissolved gases. Later magma moved
towards the surface of the earth and pushed iron present in the mantle. Atmosphere
was still typically reducing in nature, due to the presence of high concentrations of
reducing gases (H2S, H2, CH4) and was characterized by the absence of free oxygen.

Towards the later era of stage II, iron moved to the core and so the ejected gases
did not get to interact with iron and so they were more oxidizing in nature. These
included CO2, SO2 and H2O vapours. However, free oxygen was still absent and
the atmosphere continued to be reducing, non oxidizing in nature. In due course of
time, oxidising action of atmosphere resulted in the formation of iron oxides which
incorporated into sediments, forming redbed.

StageIII
In the third stage, the present atmosphere, oxygen production began to exceed
oxygen consumption via photochemical dissociation of water molecules. Water
molecules, in the upper atmosphere, absorbed ultraviolet radiations and split
into hydrogen and oxygen. Oxygen was majorly accumulated in the atmosphere
through photosynthesis. Multi-cellular marine organisms appeared during this
period. They consumed phytoplankton and floated on the water. With the decrease
of phytoplankton, the number of heterotrophic bacteria also declined. This led to an
increase in the oxygen in the atmosphere.

5.3 COMPOSITION OF ATMOSPHERE

The current atmosphere is a mixture of gases containing nitrogen (78.08% by
volume), oxygen (21%), argon (about 0.93%) and carbon dioxide (0.03%) as the
main components (Table 1). Except for water vapour whose atmospheric abundance
varies from 0.1 to 4%, the proportions of other gases remain nearly uniform below
an altitude of about 100 km. In addition, air contains trace amounts of gases like
neon, helium, methane, krypton, nitrous oxide, hydrogen, xenon, sulphur dioxide,
ozone, iodine, nitrogen dioxide, ammonia, and carbon monoxide, at levels below
0.002%. The mass of atmosphere at present is estimated to be about 5.6 x 1014
tonnes.

The atmospheric gases fall into three categories based on their abundance: major,
minor, and trace. Nitrogen and oxygen, major components, together constitute
approximately 99% of the atmosphere. Nitrogen accumulated over time as a result
of its chemical inertness and high molar mass that prevented escape from the region
of the earth’s gravitation. It is believed that denitrifying bacteria in marine sediments
serve as the major route for the return of nitrogen to the atmosphere. Oxygen is
almost entirely of biological origin and is exchanged between the atmosphere and
life through the processes of photosynthesis and respiration.

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Chemistry of Air, Carbon dioxide, ozone, methane and noble gases like neon, helium, argon, krypton
Water and Soil and xenon are present in minor quantities. Argon gas originates from the decay of
radioactive potassium K-40 in the mantle and crust. Other noble gases are very inert
and do not generally engage in any chemical transformation within the atmosphere.
Hydrogen is likewise present in trace quantities in the atmosphere, but since it is
so light, after some time much of it has escaped Earth’s gravitational pull to space.
Ozone and carbon monoxide concentrations vary with time and location. Ozone is
formed by the reaction of O2 with oxygen atoms produced photochemically. The
concentration of ozone varies with the time of day, the concentration of oxygen atoms
from other sources (photochemical smog) and with altitude. The concentration of
ozone reaches a maximum of 12 ppm at a height of 15-20 km. The concentration
of carbon dioxide is increasing at a rate of 0.2-0.7% per year as a result of burning
of fossil fuels. However, major amounts of CO2 are of natural origin and represent
the smallest part of the total carbonate reservoir that includes oceanic CO2, HCO3–,
and carbonate sediments.

The most abundant gases in the troposphere include carbon dioxide, methane, nitrous
oxide, water vapour and ozone which are involved in the Earth’s natural greenhouse
effect that keeps the planet warmer than it would be without an atmosphere. Through
emissions of greenhouse gases however, mankind has enhanced the greenhouse
effect which may now be leading to a warming of the Earth’s temperatures.

Table 1. Composition of atmosphere

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5.4 STRUCTURE OF ATMOSPHERE Atmospheric
Chemistry
Structure of the atmosphere is classified on various criteria

In this section, we shall discuss classification of atmosphere into four different

layers based on its temperature profile. The temperature profile of atmosphere is
controlled mainly by the degree of absorption of solar radiations in various regions.
The vertical temperature profile of the atmosphere is shown in Figure 1. The table
2 gives the temperature range of various regions of the atmosphere. In general, the
atmosphere is not heated by the sun’s rays but rather heated from the warm Earth.
Temperature thus decreases with increasing altitude and any change in this trend is
due to the presence of species that absorb solar radiations directly.

Let us understand each region in detail for their composition and general behaviour.

Table 2. Temperature variations in different regions of atmosphere

Region Altitude range (Km) Temperature range (°C)
Troposphere 0 – 11 15 to -56
Stratosphere 11 – 50 -56 to -2
Mesosphere 50 – 85 -2 to -92
Thermosphere 85 - 500 -92 to 1200

1. Troposphere
The troposphere extends from sea level to a height of 11 km and includes the 1
km layer closest to the earth’s surface in which life exists. The densest layer of the
atmosphere, troposphere contains about 80% of the atmospheric mass, contributed
by nitrogen, oxygen, carbon dioxide, argon, water vapours (0.1 to 5%) and traces
of helium, neon, nitrous oxide, krypton, carbon monoxide, hydrogen, ozone and
methane. Apart from these gases, the troposphere is also laden with particulate
matter from several hundred/ cm3 (in pure air) to about a lakh/ cm3 (in polluted
air). Size of these particles also varies from 0.1 to 10 Solid or liquid particles of
dimensions less than 0-1 suspended in air are called Aitken particles.

The troposphere is characterized by the presence of thermally induced turbulent

conditions which give rise to fluctuations in temperature and precipitation that is
collectively referred to “weather.” Tropo means change and almost all the changes
we experience in our daily weather occur in this layer of the atmosphere. Radiations
from the Earth heat the air near the ground level and as the altitude increases, there
is a drop in temperature. In this context, a term called Lapse rate is used which is
defined as the rate of change of temperature with altitude. For a dry ideal gas, the
lapse rate, called dry Adiabatic Lapse rate, is -9.8 K/ km. Considering the presence

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Chemistry of Air, of water vapour that condenses to ice/ snow and release heat as rising air expand,
Water and Soil the lapse rate in this region rises to -6.4 K/ Km. Essentially, the negative lapse rate
indicates that temperature decreases with altitude in this region.

Figure 5.1 Variations in temperature of the atmosphere with altitude

The boundary between troposphere and stratosphere is called tropopause where

the lowest temperature is reached. Tropopause marks temperature inversion and
serves as a barrier causing water vapour to condense to ice, preventing it from
reaching altitudes at which it would photo-dissociate through the action of high
energy UV radiations. If this happened, hydrogen produced would escape into
earth’s atmosphere and get lost.

2. Stratosphere
The layer of the atmosphere above troposphere is called stratosphere, extending
from about 11 km to about 50 km above the sea level. This layer is practically free
from clouds and related weather phenomenon, making conditions perfect for flying
planes. The most significant feature of this layer is that it shows a positive lapse
rate with the temperature increasing to -2 °C. The region is rich in ozone with a
concentration range of 10-15 ppm, forming a layer at around 20 km altitude called
ozonosphere. The warming up tendency of Stratosphere is due to ozone molecules
absorbing solar UV radiations (λ =190-340 nm). These are the UV-B radiations
which, if not absorbed by ozone, would reach the surface of Earth and cause harm
to life. Hence, this thin layer of ozone is extremely important, acting as a protective
shield from the toxic effects of UV-radiations on living beings on this planet.

Reactions for the formation of ozone and its absorption of UV-B radiation:

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Thus, the formation of ozone and oxygen is a cyclic phenomenon. Atmospheric
Chemistry

The formation and destruction of ozone is a natural process, involving absorption

of UV radiation and consequent release of heat. It is the heat that reduces the
cooling effect and changes the lapse rate from negative to positive. Stratopause
represents boundary between stratosphere and mesosphere, that depicts upper end
of temperature inversion.

3. Mesosphere
The layer of atmosphere that follow stratosphere is known as mesosphere, extending
from about 50 km above the sea level to about 85 km. This layer is characterized by
the absence of radiation-absorbing species, resulting in a decrease in temperature
to about -92 °C with increasing altitude. Apart from cold temperature, there is very
low atmospheric pressure. Mesopause is the extremely cold, boundary between
mesosphere and thermosphere which denotes the start of temperature inversion.

4. Thermosphere
The uppermost layer of the atmosphere, thermosphere, where artificial satellites
orbit the earth. This layer is present at altitudes of several hundred km. It consists of
minor concentrations of oxygen ions (O+), molecular oxygen (O2+) and molecular
nitrogen ions (N2+) which can effectively absorb UV-radiations. Hence with
increasing altitude, temperatures as high as 1200 °C are observed by the absorption
of electromagnetic radiation (λ < 200 nm) by the gaseous species in this region.

Figure 5.2 Major regions of the atmosphere

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Chemistry of Air, Check Your Progress I
Water and Soil
Notes: (a) Write your answer in about 50 words
(b) Check your progress with possible answer at the end of the unit.

How was the present atmosphere formed. What factors were responsible for
the atmosphere to become oxidizing in nature?

What is the present composition of the atmosphere

What do you understand about the temperature profile of the zones of the
atmosphere

5.5 ATMOSPHERIC STABILITY

The temperature profile of atmosphere is of utmost importance in determining
the stability and hence the degree of mixing of pollutants in various regions and
atmosphere as a whole.

5.5.1 Atmospheric lapse rate

Imagine an insulated balloon, that doesn’t exchange heat with the surroundings. As
the balloon rises, it expands due to a decrease in atmospheric pressure. Expansion
results in cooling of gas, so the temperature of air inside the balloon decreases.
The layer of atmosphere closest to the earth surface is warm due to absorption of
solar radiations. As warm air rises above cold air at the same pressure, it undergoes
expansion owing to its lower density. Thus, it undergoes adiabatic expansion (no
exchange of energy with surroundings) and becomes cooler. The rate of change
in temperature of atmosphere with elevation is known as Lapse rate, denoted by
the Greek capital letter Gamma (Γ). The lapse rate is taken negative when the
temperature decreases with altitude, zero when the temperature is constant with
altitude and positive when the temperature increases with altitude. Adiabatic Lapse
Rate is the rate of fall in temperature of a rising air adiabatically and involves
temperature changes due to the rising or sinking of an air parcel. Adiabatic lapse
rates are usually categorized as dry or moist.

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 Atmospheric
Chemistry

5.5.2 Types of lapse rates

The lapse rates used to express the rate of temperature change with a change in
altitude are follows:
i. Dry adiabatic lapse rate
ii. Wet adiabatic lapse rate

i. Dry adiabatic lapse rate

Earth’s atmospheric air is rarely completely dry. It usually contains some amount
of water vapour and when it contains as much water vapour as it is capable of, it
is referred to as saturated air (i.e., a relative humidity of 100%). The dry adiabatic
lapse rate (DALR) refers to the lapse rate of unsaturated air (i.e., air with a relative
humidity of less than 100%). If there is no condensation of moisture from air, the
cooling effect is about 10 °C per 1000 metres of altitude. For the earth’s atmosphere,
dry adiabatic lapse rate for the is 9.8 °C/km. It depends on the specific heat capacity
of air at constant pressure, Cp and the acceleration due to gravity, g. Owing to low
moisture content, it is mainly associated with stable conditions.

Γd =

Since g and Cp vary little with altitude, the dry adiabatic lapse rate is approximately
constant in the troposphere.

ii. Wet adiabatic lapse rate

When there is sufficient moisture in rising air, water condenses out from it and
releases latent heat. This offset the cooling effect of the expanding air, resulting in
a moist adiabatic lapse rate (WALR). The moist adiabatic lapse rate is not constant
and varies considerably due to presence of variable amounts of water vapour in the

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Chemistry of Air, air. The greater the amount of vapour, the smaller the adiabatic lapse rate because
Water and Soil condensation process keeps on adding more latent heat of condensation. In the
troposphere, the rate varies from about 4 °C / km in regions where the ambient
temperature is about 25 °C to about 7 °C/ km in middle of the troposphere. On
average, it is taken as 6 °C/km. As air rises and cools, it may eventually lose
its moisture through condensation, lapse rate then increases and approaches the
dry adiabatic value. Wet Adiabatic Lapse rate is mainly associated with unstable
conditions because of higher moisture content.

5.5.3 Lapse rates and atmospheric stability

Atmospheric gases move horizontally and/or vertically from regions of high
atmospheric pressure to low atmospheric pressure. Air at one altitude would mix with
air at another altitude. This phenomenon is known as vertical mixing. Atmospheric
stability is the resistance of the atmosphere to the vertical mixing of air. The rate
of change of atmospheric temperature with increasing altitude (temperature lapse
rate) is important in understanding the atmospheric stability and degree of mixing
in a particular atmospheric layer.

The atmospheric stability may be characterized as follows:

• A very stable atmosphere is one that has very little if any, vertical mixing of
the air.
• A stable atmosphere is one that inhibits vertical mixing but does have some
motion of the air.
• An unstable atmosphere is one that encourages continual vertical mixing of the
air, upwards or downwards.
• A neutral atmosphere is one that neither discourages nor encourages vertical
mixing of the air and is often referred to as conditionally stable.

The stability of atmosphere is determined by the relative numerical value of

environmental lapse rate in comparison with either the dry or moist adiabatic lapse
rates.

• Case 1: Γ > Γd
When the temperature of the atmosphere decreases faster with altitude than the
adiabatic lapse rate, then the atmosphere is turbulent in the atmosphere and the
atmosphere is said to be unstable. It may also be referred to as being super-adiabatic.
The air from one altitude mixes with the air from other altitudes. This feature is
responsible for dispersal of pollutants (vertical mixing) and becomes desirable
from viewpoint of controlling air pollution as pollutants will rapidly be dispersed
throughout the atmosphere.

• Case II: Γ < Γd

When the temperature decreases less rapidly with altitude than the adiabatic lapse
rate, the air is stable. It may also be referred to as being sub-adiabatic. Under
these conditions, there is very little movement of air from one altitude to another
so pollutants in the air will be restricted. Without vertical mixing, pollutants
concentration rises rapidly.

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• Case III: Γ = Γd Atmospheric
Chemistry
When the actual temperature gradient is same as that of adiabatic lapse rate,
neutrally stable environment

Temperature inversion, the extreme case, occurs when the temperature increases
with altitude resulting in a stable atmosphere. As shown in figure 3, the adiabatic
lapse rate thus represents a boundary between atmospheric stability and instability.

Figure 5.3 Adiabatic lapse representing a boundary between atmospheric stability and
unstability.

According to perfect gas law, P= ρRT

Ρ = pressure
ρ = density
R = gas constant
T = absolute temperature

Imagine an insulated balloon suspended in the atmosphere, the pressure of air inside
the balloon-
Pb = ρbRTb

And pressure of air outside the balloon, Pb = ρaRTa

If balloon is at particular altitude, neglecting any effect caused by air resistance,

then
Pa = Pb
OR ρb = ρa

Under stable atmospheric conditions, the balloon will remain suspended at a

constant altitude and will resist any motion under influence of external forces.

At position 1, balloon having the same internal temperature and pressure as the
surrounding atmosphere (Figure 4). When the balloon is raised to position 2, the
pressure inside the balloon falls and balloon expands. Hence, balloon’s temperature

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Chemistry of Air, drops. For Tb < Ta, we have ρb > ρa. Thus, the density of air inside balloon is greater
Water and Soil than the surrounding air and balloon will therefore be pushed to its original position
1. Similarly, balloon is lowered from position 1 to position 3, when Tb > Ta and
ρb < ρa i.e when air inside the balloon becomes less dense than the surrounding
atmosphere.

Figure 5.4 Raising the balloon from position 1 to position 2 causes the density inside greater
than the density outside, so balloon returns to position 1. Lowering the balloon to position 3
causes the density of the balloon’s air to be less than the density of atmosphere so it returns
to position 1. This represents a stable atmosphere.

5.5.4 Importance of understanding atmospheric stability

The difference between the normal lapse rate and the dry and moist adiabatic lapse
rates determines the vertical stability of the atmosphere. It also decides the movement
of an air particle to return to its original position or to accelerate away from its
original position once it is given a small vertical displacement. The lapse rate is of
importance to meteorologists in forecasting cloud formations, thunderstorms, and
the intensity of atmospheric turbulence.

Atmospheric turbulence and mixing play a major role in dispersal of air pollutants.
The phenomenon of turbulence and mixing are dominant under unstable atmospheric
conditions and promotes the dispersion of air pollutants. On the contrary, stable
atmosphere represses turbulence and results in very poor dispersion of air pollutants.
A stable atmosphere prevents rainfall, while an unstable atmosphere encourages
thunderstorm and rainfall. A stable atmosphere also prevents forest fires; thus,
an understanding of atmospheric stability is important in explaining forest fire
behaviour.

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5.6 CHEMICAL AND PHOTOCHEMICAL Atmospheric
Chemistry
REACTIONS IN THE ATMOSPHERE
The study of atmospheric reactions is an important area in understanding the
mechanistic details of chemical processes occurring in the air. The two most important
parameters in atmospheric chemistry are the sun’s radiation, predominantly in the
ultraviolet region of the spectrum and the hydroxyl radical. The former acts a source
of high energy to a single gas molecule to start a series of atmospheric reactions and
latter serves as the most important reactive intermediate and reservoir of daytime
atmospheric chemical phenomena.

Gaseous atmospheric species can be classified as follows:

• Inorganic oxides- CO, CO2, NO2, SO2
• Oxidants- O3
• Reductants- CO, SO2, H2S
• Organics- CH4, some alkenes and aryl compounds
• Photochemically active species- NO2, formaldehyde
• Acids (H2SO4), Bases (NH3), salts (NH4HSO4)
• Unstable reactive species- HO.͘ radical, electronically excited NO2,

In addition, both solid and liquid suspended particles play a significant role as
source and sink for gas-phase species, as sites for surface reactions (solid particles)
and as media for aqueous phase reactions (liquid droplets).

5.6.1 Photochemistry of the atmosphere

The most significant attribute of atmospheric chemistry is the occurrence of
photochemical reaction, a chemical reaction initiated upon the absorption of
light photons by the reactant molecules. The energy, E, of a photon of visible or
ultraviolet light is given by the equation E = hν, where h is Planck’s constant and
ν is the frequency of light. As a consequence, energy associated with absorbed
photons is sufficient to activate reactant molecules. The transient excited states
of reactant molecules thus formed, differ in chemical and physical properties
from the original molecules. The chemical species thus formed either transform
to new molecules, combine among themselves or other molecules, or transfer
electrons, hydrogen atoms, protons, or their energy to other molecules (Figure 5).
The photochemical reactions play a crucial role in determining the nature and fate
of chemical species in the atmosphere. Nitrogen dioxide, NO2 is one of the most
photochemically active species present in polluted air and a major contributor to
smog formation. On absorption of light energy (E = hν) in the visible or UV region
of the electromagnetic spectrum, NO2 yields electronically excited molecule,

NO2 + hν → NO2*

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Chemistry of Air,
Water and Soil

Figure 5.5 A schematic representation of atmospheric chemical processes.

The nature of excited state may be understood by considering addition of electrons

in a molecule. Most molecules contain even number of electrons. The electrons tend
to occupy the orbitals, with maximum two electrons with opposite spins per orbital.
On absorption of light of sufficient energy, one of these electrons may promote
to high energy vacant orbital. In some cases, the promoted electron retains a spin
opposite to that of its former partner, giving rise to an excited singlet state. While in
some cases, the promoted electron experiences a spin reversal, such that it has same
spin as that of its former partner, giving rise to excited triplet state.

These energetic excited species are chemically reactive and are actively involved in
atmospheric reactions which are discussed in detail in the following sections.

Following the light absorption, the electronically excited molecules lose their
excess energies in either of the following reactions-

Energy loss to another atom or molecule by physical quenching and dissipation of

energy as heat
O2* + M + hν → O2 + M (higher translational energy)

• Dissociation of the excited molecule

O2* + hν → O + O

• Direct reaction with another species- The energy released during de-excitation
is sufficient for the reaction to take place.
O2* + O3 + hν → 2O2 + O

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• Luminescence – loss of energy upon emission of electromagnetic radiation Atmospheric
Chemistry
NO2* + hν → NO2 + hν

The phenomena of luminescence with instantaneous re-emission of light is known

as Fluorescence. In case, if it is significantly delayed, phosphorescence takes place.
Chemiluminescence takes place when there is a formation of excited intermediate,
which de-excites, releasing some of its energy in form of light.
O3 + NO + hν → NO2* + O2 (higher energy)

• Intermolecular energy transfer wherein energy is transferred from excited

species to other species, which then becomes excited.
M* + Y + hν → M + Y*

A photosensitized reaction may take place when the second species so generated
participates in chemical transformations.

• Intramolecular transfer, wherein energy is transferred within the molecule

itself.
XY* + hν → XY† (where † stands for excited state of the same molecule)

• Spontaneous isomerization, as seen in the conversion of o-nitrobenzaldehyde to

o-nitrosobenzoic acid, a reaction employed in chemical actinometers to measure
exposure to electromagnetic radiation.

• Photoionization, depicts formation of ionic species with a loss of an electron

N2* → N2+ + e-+ hν

• Photodissociation – radicals are produced

N2 + hν → Ν• + Ν•

Electromagnetic radiation absorbed in the infrared region are not sufficiently high
in energy to be capable of breaking the chemical bonds. However, they provide
sufficient vibrational and rotational energy to the receptor molecules. The energy
absorbed as infrared radiation ultimately is dissipated as heat and raises the
temperature of the whole atmosphere

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Chemistry of Air, 5.7 DISTRIBUTION OF SPECIES IN
Water and Soil
ATMOSPHERE
Other than gaseous species, atmosphere also comprises of ions, free radicals and
particulate matter. A detailed account of these species is discussed in the following
sections.

5.7.1 IONS IN THE ATMOSPHERE

The layer of atmosphere extending from about 50 km above sea level constitutes
the ionosphere. The importance of ionosphere is realised by the fact that it reflects
and modifies radio waves used for communication and navigation. The height,
concentration of ionized particles, and the existence of the different regions of
the ionosphere varies with time. During the day, X-rays and ultraviolet radiation
from the Sun provide sufficient energy to knock off electrons free from atoms and
molecules, producing a continuous supply of ions and free electrons. The principal
ions present in this region are N2+, O2+, NO+, N+ and O+. At the same time, some
of the ions and electrons collide and re-combine to form electrically neutral atoms
and molecules. In dark, positive ions may recombine with free electrons. This
phenomenon is rapid in lower regions of the ionosphere where the concentration
of species is high. Thus, radio waves are bounced off by lower regions of the
ionosphere and are transmitted over greater distances at night.

The ions do not escape from the ionosphere as they are strongly bound by Earth’s
magnetic field. One of manifestation of the influence of Earth’s magnetic field on
these ionizing particles is called Van allen belts. These belts are named after the
scientist, Dr James Van Allen who is credited for their discovery. Van Allen Belts
consists of a zone of high energy charged particles, held by the earth’s magnetic
field around the planet. If they are visualised as two doughnuts, then the axis of the
earth’s magnetic field extends through the holes in the doughnuts (Figure 6). The
belt is divided into another two belts – outer and inner. The outer belt is formed
by the electrons while the inner belt consisting of protons is formed as a result of
cosmic ray collisions in the upper atmosphere.

Figure 5.6 Cross section of the Van Allen Belts encircling the Earth.

5.7.2 Free radicals in the atmosphere

Atoms or groups of atoms with unpaired electrons called radicals are generated in
the atmosphere by high energy electromagnetic radiations. Free radicals exhibit

136
high reactivity by virtue of the strong pairing tendency of unpaired electrons. They Atmospheric
participate in chain reactions wherein one of the products of each reaction is itself a Chemistry
radical. The termination of chain is marked by the reaction of a radical with another
radical (chain-terminating reaction).

It is worthy to mention that free radicals and single atoms from diatomic gases
are quite stable and may have half-lives of several minutes such that they persist
under the rarefied conditions of the upper atmosphere. At high attitudes, these
species travel long distances before colliding with other reactive species. On the
other hand, electronically excited species are short-lived because their energy is
lost through radiation, instead of reacting with another species. Some important
radicals in atmosphere are hydroxyl (HO•), Hydroperoxy (HOO•) and alkylperoxy
(H3COO•) radicals. In this section, the atmospheric chemistry of the most prevalent
hydroxy (HO•) and Hydroperoxy (HOO•) radicals are discussed in detail.

• Hydroxyl and Hydroperoxyl radicals in the atmosphere

The hydroxyl radical OH•, the most important reactive species in chemical reactions
of the atmosphere. It is usually produced by photolysis of water at higher altitudes.
H2O + hν → HO• + H

The production of HO• radical depends on the wavelength of light and availability
of the substrate. Therefore, the concentration of HO• radical increases during
summer and geographically tropical areas where the high humid conditions favour
HO• formation. The diurnal plot of the variation of concentration of HO• radical
with the daytime is shown in figure 7. The plot indicates that the concentration of
HO• radical is maximum during afternoon and gradually decreases during night.
Globally, the averaged diurnal and seasonal concentration of tropospheric HO•
ranges from 2 ꓫ 105 to 1 ꓫ 106 radicals per cm3.

Figure 5.7 Average diurnal profiles of the hydroxyl radical

Under laboratory conditions, HO• radical is generated by the photolysis of nitrous

acid vapour and hydrogen peroxide
HONO + hν → HO• + NO
HOOH + hν → 2HO•

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Chemistry of Air, The radical is also produced by photolysis of ozone, wherein the reaction proceeds
Water and Soil with the formation of excited oxygen atoms that combine water molecules to yield
hydroxyl radical.
O3 + hν(λ < 315 nm) → O* + O2
O* + H2O → 2HO•

It is also produced as an intermediate during the formation of photochemical smog,

which will be discussed in detail in block III.

Figure 5.8 Central role of OH• radical in the troposphere.

Hydroxyl radical bearing unpaired electron is highly unstable and extremely

reactive. Therefore, it enters into several reactions with variety of species present
in atmosphere. Some of the important reactions are summarised in figure 8.

Sinks for removal of Hydroxyl radical

A sink refers to a medium that comprises of molecules that react with the species
in question in order to make them potentially less harmful. For OH• radical, there
are two sinks, methane or carbon monoxide, that eliminate it from the troposphere.
CH4 + HO• → H3C• + H2O

The methyl radical is highly reactive and forms methylperoxyl radical, H3COO͘͘•
upon reaction with O2
H3C• + O2 → H3COO•

Similarly, reaction with carbon monoxide produces atomic hydrogen, which then
reacts with O2 and results in the formation of hydroperoxyl radical HOO•.
CO + HO• → CO2 + H
H + O2 → HOO•

138
The hydroperoxyl radical undergoes series of chain termination reactions, either Atmospheric
with radicals, Chemistry

HOO• + HO• → H2O + O2

HOO• + HOO• → H2O2 + O2

Or with neutral species that regenerate hydroxyl radicals.

HOO• + NO → NO2 + HO•
HOO• + O3 → 2O2 + HO•
The hydroperoxyl radical may be regenerated through reaction with formaldehyde,
a major organic molecule present in atmosphere. Photolytic dissociation of
formaldehyde furnishes formyl radical, as the reactive intermediate, that combines
with atmospheric oxygen to produce hydroperoxyl radical.

The hydroperoxyl radical, HOO• serves as an important intermediate in variety of

chemical reactions. However, hydroperoxyl radical reacts slowly with other species
than hydroxy radical, OH•. Thus, kinetic studies pertaining hydroperoxyl radical
are difficult to study because these radicals hardly exist without hydroxyl radicals.

Check Your Progress II

Notes: (a) Write your answer in about 50 words
(b) Check your progress with possible answer at the end of the unit.

1. What is the relation between atmospheric stability and vertical mixing

2. Differentiate between

Chemiluminescence and Luminescence

139
Chemistry of Air, Wet and dry adiabatic lapse rate
Water and Soil

3. Discuss the importance of ionosphere.

---------------------------------------------------------------------------------------------------

4. Describe the mechanism for the production of OH• radicals in the

troposphere. How would you expect increasing temperature to influence water
vapour concentrations and hence the efficiency of OH• production?

5. Which species are responsible for the removal of hydroxyl radical from
the unpolluted troposphere?

5.8 REACTIONS OF ATMOSPHERIC OXYGEN

Oxygen in the atmosphere, especially in the troposphere, is crucial for survival of
lifeforms. A schematic representation of the oxygen cycle depicting biogeochemical
reactions of oxygen within atmosphere, lithosphere, hydrosphere and biosphere is
shown in figure 9. Oxygen plays a dominant role in the processes occurring on the
surface of earth. It drives the energy producing reactions, for example, the burning
of fossil fuels.
CH4 (in natural gas) + 2O2 → CO2 + 2H2O

140
Aerobic organisms rely on atmospheric oxygen for degrading organic matter. Atmospheric
Oxygen also plays a crucial role in chemical weathering processes. Chemistry

4FeO + O2 → 2Fe2O3

Oxygen is returned to the atmosphere through photosynthesis by green plants and

planktons.
CO2 + H2O + hν → {CH2O} + O2

It can be shown that most of the carbon fixed by photosynthetic processes is dispersed
in mineral formations as humic material, while only a small portion is deposited in
fossil fuel beds. Thus, the oxygen production and consumption constitute a cyclic
phenomenon, maintaining global oxygen levels constant.

Figure 5.9 Oxygen exchange among the atmosphere, lithosphere, hydrosphere and biosphere.

Molecular oxygen displays unusual behaviour that its ground state is a triplet state
with unpaired electron, denoted as 3O2 which can be excited to singlet molecular
oxygen, 1O2. Singlet oxygen may also be produced by other processes such as direct
photochemical excitation, transfer of energy from other electronically excited
molecules, ozone photolysis and high-energy oxygen producing reactions.

Under ionizing atmospheric conditions, elemental oxygen in the upper atmosphere

exists in allotropic forms other than diatomic O2 molecule. Thus, in addition to O2,
the upper atmosphere contains oxygen atoms, O; excited oxygen molecules, O2*
and ozone, O3. Atomic oxygen is produced via photochemical reaction, as follows.
O2 + hν → O + O

The energy of ultraviolet radiation in the wavelength regions 135-176 nm and 240-
260 nm is sufficient to dissociate oxygen-oxygen bond in diatomic O2 molecule
(bond energy of O2 =120 kcal/mol). Because of photodissociation, O2 does not
exist at very high altitudes and only less than 10% of the oxygen is present in
its molecular form in the atmosphere at altitudes exceedingly approximately 400

141
Chemistry of Air, km. A manifestation of this phenomenon of high atomic oxygen concentration is
Water and Soil realised by the fact the average molecular weight of air is lower than 28.97g/mole,
observed at sea level at altitudes above 80 km.

In the atmosphere, oxygen atoms exist in the ground state (O) as well as in excited
states (O*) and are mainly produced through photolysis of ozone. The dissociation
enthalpy required to dissociate oxygen-oxygen bond in a molecule of ozone is
relatively low (26 kcal/mol) and thus facilitates the quick formation of excited
oxygen atoms.
O3 + hν(λ < 308 nm) → O* + O2

The highly energetic chemical reactions also allow for the formation of excited
oxygen atoms that emit visible light at wavelengths 636 nm, 630 nm and 558 nm.
The light so emitted is said to be partially responsible for airglow, luminescence of
earth’s upper atmosphere.
O + O + O → O2 + O*

Oxygen ion, O+, may be produced by action of ultraviolet radiations on oxygen

atoms. These are predominant species in some parts of ionosphere. Oxygen ion
participates in reactions with neutral species like, N2 or O2, and releases other
positive ions.
O + hν → O+ + e-
O+ + O2 → O2+ + O
O+ + N2 → NO+ + N

O2+ ion may be produced in the intermediate regions of ionosphere upon absorption
of light of wavelength 17-103 nm by O2 molecule or from photochemical reaction
of low energy X-rays.

5.9 REACTIONS OF ATMOSPHERIC OZONE

Ozone forms a protective layer that envelops the earth surface by absorbing the
sun’s ultraviolet radiations (220-330 nm) which otherwise would potentially
damage life forms on the earth. The presence of ozone in higher atmospheric
layers is attributed to the photodissociation reactions of molecular oxygen. Upon
absorption of ultraviolet radiation from the sun, oxygen molecule splits as follows:
O2 + hν → 2O
O + O2 + M → O3 + M + Heat

Where M is the third body, such as a molecule of N2, O2 or Ar that allows formation
of ozone by absorbing heat energy released during collision between atomic oxygen
and oxygen. Some of the oxygen atoms react with intact ozone molecules to destroy
them by concerting to O2.

142
 O + O 3 → 2 O2 Atmospheric
Chemistry
However, the above reaction is very slow because its activation energy is 18 kJmol-1.
To summarise, during daylight, ozone in the stratosphere is constantly being formed,
decomposed and re-formed by a series of reactions. Ozone’s concentration at any
time of the day depends on the intensity of solar radiation and the altitude. The
maximum ozone concentration of about 12 ppm is observed at altitude of 25-30 km
in the stratosphere.

Oxygen and ozone filter out harmful ultraviolet radiation, such that incoming
radiation in troposphere has wavelength ≥ 290 nm. This incoming light possess
sufficient energy to allow photodissociation of key tropospheric species. The heat
energy released in the above reaction is responsible for the increase in temperature
with altitude in the stratosphere. As discussed in section 1.3, the air at a given
altitude in stratosphere is cooler than air lying above it. Cooler air is denser than
the hot air, therefore it doesn’t rise spontaneously under influence of gravity. As a
result, vertical mixing of the air in stratosphere is a very slow process as compared
to that in the troposphere.

Catalytic process for ozone destruction

The decomposition reaction:

2O3 → 3O2

is thermodynamically favourable, indicates ozone is unstable. The reaction is

catalysed by pollutant trace constituents, NO, NO2, H, HO•, HOO•, ClO•, Cl, Br,
and BrO•. In addition, stratospheric ozone undergoes reaction with atomic oxygen,
hydroxyl radical and NO.
O3 + hν → O2 + O
O3 + O → O2 + O2
O3 + HO• → O2 + HOO•

The following reaction regenerates HO• radical and further contributes to the
decomposition of ozone.
HOO• + O → HO• + O2

Similarly, nitric oxide, one of the key pollutants in troposphere is also held
responsible for the destruction of ozone in stratosphere.
O3 + NO → NO2 + O2

NO, so consumed during this reaction is recycled through the following reaction
NO2 + O → NO + O2

Atmospheric N2O also accounts for the release of nitric oxide in the atmosphere.
N2O + O → 2NO

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Chemistry of Air, N2O occurs naturally in the atmosphere and constitutes a major product of the
Water and Soil denitrification process wherein fixed nitrogen is returned to the atmosphere in
gaseous form.

Despite its role as a protective shield in the stratosphere, tropospheric ozone is

considered as an undesirable air pollutant and is harmful to human and ecosystem
health. The details about its role as a pollutant will be discussed in detail in Block
III.

5.10 REACTIONS OF NITROGEN OXIDES

Nitrogen constitutes about 78% by volume of the earth’s atmosphere, representing
an inexhaustible reservoir of the essential element. Due to high bond dissociation
energy (945 kJmol-1), N2 molecule is chemically and photochemically unreactive.
Thus, unlike oxygen which dissociates completely into oxygen atoms in the higher
regions of thermosphere, nitrogen molecule does not dissociate upon absorption of
ultraviolet radiation. However, atomic nitrogen is formed through photochemical
reactions at high altitudes exceedingly approximately 100 km.
N2 + hν → N + N (photodissociation)

Other reactions producing atomic nitrogen are

N2 + hν → N2+ + e- (photoionization)
N2+ + O → NO+ + N
NO+ + e- → N + O
O+ + N2 → NO+ + N
NO2 + O → NO + O2

In the above reactions, N2+ is formed by photoionization when N2 molecule absorbs

a photon of light in the lower regions of the ionosphere, extending from about 50-
85 km in altitude. In higher regions, the chief ionic species is NO+ generated from
ionization of NO. NO is a colourless and odourless gas and is very reactive owing
to its radical nature.

Of the eight known oxides of nitrogen, three oxides are present in appreciable
amount in the atmosphere – Nitrous oxide, N2O; nitric oxide, NO; nitrogen dioxide,
NO2. NO and NO2 (collectively referred to as NOx) are common air pollutants
owing to their potential involvement in the stratospheric destruction of ozone layer,
formation of photochemical smog and acid rain. The principal reactions of nitrogen
oxides are outlined in figure 10.

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 Atmospheric
Chemistry

Figure 5.10 A schematic view of principal reactions among NO, NO2 and HNO3 in the
atmosphere (ROO• denotes an organic peroxyl radical)

Nitric oxide, NO, through a series of photochemical reactions, enters the atmosphere
from N2O or NO2 and oxygen atom. Other natural sources like lightning strikes,
forest fires or volcanic eruptions also contribute to NO formation. The main
anthropogenic sources of NO, contributing to 96% of total NOx in atmosphere are
the burning of fossil fuel in furnaces, factories and automobiles. At extremely high
temperatures of these natural phenomena or inside the internal combustion engines,
nitrogen and oxygen molecule react to give NO.
N2 + O2 → 2NO

Elevated temperatures are favourable for a high equilibrium concentration as well

as an increased rate of formation of NO. It is postulated that at high temperatures,
the molecules of N2 and O2 dissociate to their respective atoms.
O2 + M → O + O + M
N2 + M → N• + N• + M

Where M represents a third body of high energy which itself does not react but
provides energy sufficient for enabling the reaction. The atoms then react in a chain
reaction to give NO.

In the combustion mixture, apart from N2 there are hydrocarbon fragments (RH)
which compete for highly reactive oxygen atoms.
RH + O → R• + HO•

The hydroxyl radical combines with atomic nitrogen which again leads to the
formation of NO.
N + HO• → NO + H•

NO plays an important role in the ozone content of stratosphere. It removes O3

by converting itself to NO2. NO is regenerated upon reaction of NO2 with atomic
oxygen. The details about ozone depletion will be dealt with in Block III.
O3 + NO → NO2 + O2

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Chemistry of Air, Nitrogen dioxide, NO2, is a brown gas, responsible for the colour of photochemical
Water and Soil smog. It is produced by the oxidative decomposition of ammonia in the atmosphere.
Like NO, its high reactivity is attributed to its radical nature. NO2 is finally converted
into either NO2- or NO3- in particulate matter. The particulates are then washed out by
precipitation. The dissolution of nitrate in a water droplet results in the formation of
nitric acid (HNO3), thus contributes to acid rain damage to the ecosystem. Nitrogen
dioxide participates in chemical reactions of volatile organic compounds (VOCs)
producing PAN (Peroxyaceytyl nitrate), component of smog. As shown in figure 11,
acetaldehyde is oxidized and the resulting peroxyacetyl radical reacts with NO2 to
form peroxyacetic nitric anhydride. PAN is a very irritating molecule that is toxic
to humans, animals, and plants.

Figure 5.11 A schematic representation of peroxyacetic nitric anhydride (PAN) formation

Nitrogen dioxide exists in equilibrium with its colourless dimer, Dinitrogen tetraoxide
N2O4. Its combination with water produces nitrous and nitric acids that oxidize
many metals. Being very reactive, it is an important species in the atmosphere.
It absorbs full range of ultraviolet and visible light entering the troposphere. At
wavelengths below 398 nm, photodissociation takes place and generates ground
state oxygen atoms as follows:
NO2 + hν → NO + O

At wavelength > 430 nm, only excited species are formed,

NO2 + hν → NO2*

At wavelengths between 398 nm and 430 nm, either process may take place.
Under direct sunlight, the half-life of NO2 is much shorter than that of any other
common molecular atmospheric species, hence NO2 shows high tendency to
undergo photodissociation which may give rise to series of important reactions
as summarised below. Small concentrations of NO2 have also been detected in the
lower stratosphere where the gas is produced by the oxidation of NO by ozone.

146
 Atmospheric
Chemistry

Nitrogen dioxide is removed from the atmosphere as nitric acid, nitrates, or as

organic nitrogen (in atmospheres where photochemical smog is formed). Dinitrogen
pentoxide formed in above reactions is the anhydride of nitric acid, which is formed
when the combines with water
N2O5 + H2O → 2HNO3

In the stratosphere, nitrogen dioxide combines with hydroxyl radicals and produces
nitric acid:
HO• + NO2 → HNO3

Nitric acid is destroyed by hydroxyl radicals within stratosphere,

HO• + HNO3 → H2O + NO3

or by a photochemical reaction,
HNO3 + hν → HO• + NO2

Thus, the above reactions elucidate that nitric acid serves as a temporary sink for
stratospheric NO2. Nitric acid is then removed in form of precipitation, or upon
reaction with bases (ammonia, particulate lime) forming particulate nitrates.

Nitrous oxide, N2O, also called laughing gas, is present through natural sources in
low amounts (0.3 ppm) in unpolluted atmosphere. The natural sources are microbial
activity of the soil in tropical regions and the major part is released through
activities in oceans. The gas is formed as a byproduct of denitrification reaction in
aerobic atmosphere as well as nitrification reaction in anaerobic atmosphere. For
the former, nitrogen in its highest oxidized form, i.e. NO3- is reduced to N2 and N2O
is a by-product. For nitrification, the most reduced form of nitrogen, i.e. NH4+ is
oxidized to NO2- and NO3- and N2O is a by-product. N2O is relatively unreactive
in the troposphere and its concentration decreases with altitude in the stratosphere
according to the photochemical reaction
N2O + hν → N2 + O

and reaction with singlet atomic oxygen:

N2O + O → N2 + O2
N2O + O → 2NO

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Chemistry of Air, Increased fixation of nitrogen, together with increased microbial production of N2O,
Water and Soil contributes to depletion of ozone layer. Other neutral nitrogen oxides present in the
atmosphere include N2O5 and N2O3. Ammonia and other volatile organic amines,
released upon decomposition of plant and animal materials, are readily oxidized to
nitrogen oxides, N2O, NO.

5.1 PARTICLES IN THE ATMOSPHERE

Several forms of particles, ranging from dust, smoke, soot, pollen, spores to micron
sized aerosols are present in atmosphere. Particulate matter or simply particles
constitute the most visible and apparent form of air pollution. It is a complex
mixture of the solid particles and liquid droplets floating in the atmosphere. Very
small, solid particles include black carbon, silver iodide, combustion nuclei, and
sea-salt nuclei formed by the loss of water from droplets of seawater, while the
larger particles comprise of cement dust, wind-blown soil dust, foundry dust, and
pulverized coal. Mist, including raindrops, fog, and sulfuric acid droplets describe
the liquid particulate matter. Other atmospheric particles of natural origin include
bacteria, pollen grains, fog and volcanic ash. A brief description about various
particles in the atmosphere is given in table 3.

Table 3. Terms describing atmospheric particles

Type Description
Aerosol Colloidal-sized atmospheric particle
Condensation aerosol Formed by condensation of vapours or reactions of gases
Dispersion aerosol Formed by grinding of solids, atomization of liquids or
dispersion of dusts
Fog high level of water droplets
Haze Decreased visibility due to the presence of particles
Mists Liquid particles
Smoke Particles released by incomplete combustion of fuel

Chemically, the particulate matter comprises of a variety of components including

acids (nitrates and sulphates), elemental carbon, metals (Mn, Cu, Zn, Cd, Cr, Fe,
Ni, K, Ca, V, Ba, As, Se, Sr), soil, fugitive dust and sea spray.

5.11.1 Characteristics of particulates

Size- The size of the particles and droplets vary. Large particles can be seen as soot
or smoke, while small particles like aerosols can only be detected with a microscope.
The particle size varies from 2 x 10-4 to 500 µm. Particles ranging from 0.001 to
10 µm in size are commonly suspended near the source of air pollution. The size
of the particle is linked to its potential causing health problems. The smaller, more
lethal is its effect. Two size ranges, PM2.5 and PM10 are frequently been monitored
at major emission sources and in air under ambient conditions. PM10 particles
have aerodynamic diameter less than or equals to 10 µm and PM2.5 corresponds
to particles with aerodynamic diameters less than or equal to 2.5 µm. These two

148
sets of particles differ in their behaviour in the atmosphere. PM2.5 or fine particles Atmospheric
tend to remain airborne for a longer time period and travel larger distances. On Chemistry
the contrary, PM10 or coarse particles, are too large to remain suspended in air and
hence rapidly deposit on the earth’s surface. Thus, particle size is a useful indicator
about the amount of time a particle remains suspended in air.
• Concentration- It varies from several hundred/cm3 to 1,00,000/cm3 and above.
The concentration at any time varies with the wind source, because the source
of release may be very far from site at which the particles are formed.
• Lifetime- Particle’s lifetime varies from few seconds to several years, that
normally happen when the particles diffuse into stratosphere. Large size
particulates have lower lifetime than small particles. The most common way
of losing their existence is by settling down. Small particles coalesce, condense
and settle down faster than larger particles.

Classification of particulates
Particulate matter is emitted directly or formed in the atmosphere. On the basis
of their origin and size, the atmospheric particles are classified as primary and
secondary particulate matter. Table 4 gives a comparison between primary and
secondary particulate matter.

Table 4. A comparison between primary and secondary particulate matter

Primary particulate matter Secondary particulate matter
Released directly into the atmosphere by wind, Released as a result of chemical
combustion processes, or human activities reactions of gaseous pollutants,
initiated either by sunlight
photochemically or with
primary particulates that act as
heterogenous reaction sites.
Belong to natural source of generation. Natural Both natural and anthropogenic
sources like forest fires, volcanic eruptions, sources. Vehicular exhaust,
dust storms, sand storms, ocean or sea sprays, combustion, construction,
biological sources-pollens, spores, microbes, mining, metallurgical operations.
meteorites.

Include suspended dust, sea salt, organic Sulphates, nitrates, ammonia,

carbon, elemental carbon, metals, small volatile organic compounds
amount of sulphate and nitrate
Coarse particles (PM10) are composed of Fine particles (PM2.5) contain
primary particulate matter secondary particulate matter

5.11.2 Chemical reactions of atmospheric particles

As discussed, secondary particulate matter is produced from chemical reactions in
the atmosphere. Oxides of nitrogen, NO2 and sulphur, SO2 are the major species
involved in the formation of the particulates. From troposphere, these particulates
diffuse into stratosphere and remain suspended at a height of 20-27 km.

149
Chemistry of Air, • Oxidation
Water and Soil
Chemistry of sulphate formation- About half of SO2 oxidation to sulphate
occurs in the gas phase through the photochemical oxidation in the daytime. NOx
and hydrocarbon emission enhance the rate of oxidation. At least half of SO2
oxidation takes place in cloud droplets. Within clouds, soluble SO2 is scavenged
by water droplets and rapidly oxidise to sulphate, forming small liquid droplets.
Mechanistically, reaction involves the gas phase oxidation of SO2(g) to H2SO4(g)
followed by condensation of H2SO4(g). Dissolution of SO2(g) in liquid water gives
H2SO3(aq),followed by conversion of H2SO3(aq) to H2SO4(aq).

Figure 5.12 Oxidation of SO2 inside water droplet

Sulphuric acid may also be formed through following reactions:

SO2(g) + 2OH• → H2SO4(g)

SO2(g) + O + M → SO3(g)
SO3(g) + H2O (aq) → H2SO4

Chemistry of nitrate formation- NO2 can be converted to nitric acid by reaction

with hydroxyl radicals during the day. The reaction of OH• with NO2 is about 10
times faster than with SO2. The peak daytime conversion rate of NO2 to HNO3 in
the gas phase is about 10-50 % per hour. During night, NO2 is converted to HNO3
in the gas phase by a series of reactions involving ozone and the nitrate radical.
NO2 + OH• → HNO3
NO2 + O3 → NO3 + O2
NO2 + NO3 → N2O5
N2O5 + H2O → HNO3

• Acid-base reaction
Both sulphuric and nitric acids droplets eventually combine with basic air pollutants
like ammonia which is released during the biological decay processes at the ground
level and lime. Acid-base reaction of these acids with ammonia affords ammonium
salts as follows,
H2SO4(droplet) + 2NH3(g) → (NH4)2SO4 (droplet)
HNO3(droplet) + NH3(g) → NH4NO3 (droplet)
H2SO4(droplet) + CaO(s) → CaSO4 (droplet) + H2O

The formation of solid aerosol is affected when water evaporates from these droplets
under low-humidity conditions.

150
Metal oxides, formed as a result of burning of fuels containing metals, represent a Atmospheric
major class of inorganic particles in the atmosphere. For example, particulate iron Chemistry
oxide is formed during the combustion of pyrite-containing coal:
3FeS2 + 8O2 → Fe3O4 + 6SO2

5.11.3 Aerosols
Atmospheric aerosols are colloidal sized solid or liquid particulates of diameter less
than 100 µm, that are suspended in the air and are in equilibrium with the gaseous
atmosphere. Particles of aerosol composed of carbonaceous material, oxides of
metal, sulphates, nitrates, ammonium salts and silicon. The composition varies with
the particle’s size. Fine, small particles originating from pollutant gases, like SO2
are acidic, while larger particles contain materials of mechanical origin, for example
grinding of limestone and thus behave as base. Aerosol particles play a crucial role
in major atmospheric phenomenon such as cloud formation, electrification and fog
formation. In the lower atmosphere, aerosols modify the size and its distribution
of the cloud droplets, thus influencing their ability to reflect and absorb sunlight.
As a result, these particles can largely regulate the earth’s energy budget. These
particles have significant influence upon visibility in the atmosphere. Particles
smaller than about 0.1 µm in diameter scatter light much like molecules, Rayleigh
scattering. Their scattering of sunlight reduces visibility (haze) and redden sunrises
and sunsets. Particles of the size ranging from 0.1 µm to 1 µm exhibit interference
phenomena because they are about the same dimensions as the wavelength of visible
light. In addition, aerosols have an outsized effect on the earth’s climate. They help
balancing the temperature of the planet by reflecting light. Very small particles
called condensation nuclei serve as templates for condensation of atmospheric
water vapor and thus play an important role in the formation of rain drops.

Aerosols can be pure compounds or complex mixtures, hydroscopic or hydrophobic.

Aerosols can transport a wide variety of inorganic and organic pollutants significant
distances if the sizes are in the submicron range. Owing to their active surface area,
the particles act as reaction sites for heterogeneous atmospheric chemical reactions.
One of the key reactions are responsible for destruction of stratospheric ozone. In
the polar regions, the aerosols grow and form stratospheric clouds. The cloud’s large
surface areas provide active sites for chemical reactions to occur. Such reactions
producing significant amounts of reactive chlorine pave the way for the destruction
of ozone in stratosphere.

5.11.4 Black carbon

Black carbon, a component of particulate matter, is emitted from diesel engines,
coal-fired power plants, and other sources burning fossil fuels. During incomplete
combustion of fuel, CO2, carbon monoxide, volatile organic compounds, organic
carbon and black carbon particles are formed. Particles of black carbon strongly
absorb sunlight and give black colour to the soot which refers to the complex
mixture of particulate matter released during incomplete combustion. It contributes
to warming by converting absorbed solar radiation to heat.

151
Chemistry of Air, Black carbon is a global environmental concern that severely affects human health
Water and Soil and climate. Inhalation of black carbon causes respiratory and cardiovascular
disease, cancer, and even birth defects. By absorbing solar radiation, black carbon
is potent contributor to global warming and is responsible for climate change.

5.11.5 Effects of particulate matter on human health

Ultra-fine atmospheric particles can travel to respiratory tract, enter the bloodstream
and release their fatal effects. Short and long-term exposure increases the risk of
lung cancer, respiratory, cardiovascular, infectious and allergic diseases. PM2.5 goes
deep inside the body and cause greater damage to the health. Studies have indicated
that each 10 µg/m3 increase in fine PM2.5 long-term exposure has been associated
with approximately 6% and 8% increased risk of cardiopulmonary and lung cancer
mortality, respectively. Other effects include, irritation of eyes, nose and throat,
severe asthma attacks, pre-term birth and low birth weight and premature death in
people with heart and lung disease.

Check Your Progress III

Notes: (a) Write your answer in about 50 words
(b) Check your progress with possible answer at the end of the unit.

What are the princiapl forms of elemental oxygen and how are these generated.

What are the oxides of N in the atmosphere and their sinks?

What are the main sources and sinks for N2O in the atmosphere?

152
What is the chemical composition of sulphate and nitrate aerosols? What is their Atmospheric
fate in troposphere. Chemistry

What do you understand by the term aerosols.Why are aerosols in the size range 0.1
to 1 µm effective in scattering light?

Differentiate between primary and secondary particles

5.12 LET US SUM UP

Earth’s atmosphere is a thin envelope of gases surrounding the solid planet. The
composition of the atmosphere consists largely of oxygen and nitrogen, as also
water vapor, carbon dioxide, methane, noble gases and some other gases in trace
amounts. The atmosphere absorbs heat from the Earth’s surface and radiate it in
all directions including back to the surface. Atmosphere has been classified into
many layers or zones on the basis of several criteria. Various chemical species,
including oxides of nitrogen, carbon and sulphur as well as their particulate matter,
present naturally and due to man’s activities undergo photochemical reactions, and
are responsible for several environmental episodes.

5.13 KEY WORDS

Troposphere Lowest and densest layer of Earth’s atmosphere extending from
sea level to 11 km high, in which most weather changes occur and temperature
generally decreases rapidly with altitude.

153
Chemistry of Air, Stratosphere The part of the earth’s atmosphere which extends from the top of the
Water and Soil troposphere to about 50 Km above the surface and in which temperature increases
gradually to about -20 C and clouds rarely form.

Mesosphere The part of the earth’s atmosphere between the stratosphere and the
thermosphere in which temperature decreases with altitude to the atmosphere’s
absolute minimum. Air in this region is very thin.

Thermosphere The region of the atmosphere above the mesosphere and below the
height at which the atmosphere ceases to have the properties of a continuous medium.
The thermosphere is characterized throughout by an increase in temperature with
height

Ionosphere The layer of the earth’s atmosphere which contains a high concentration
of ions and free electrons and is able to reflect radio waves. It lies above the
mesosphere and extends from about 80 to 1,000 km above the earth’s surface.

Ozone A triatomic very reactive form of oxygen that is a bluish irritating gas of
pungent odor, and a major air pollutant in the lower atmosphere but a beneficial
component of the upper atmosphere, and that is used for oxidizing, bleaching,
disinfecting, and deodorizing.

Adiabatic lapse rate The rate at which atmospheric temperature decreases with
increasing altitude in conditions of thermal equilibrium.

Photochemical reaction A chemical reaction initiated by the absorption of energy

in the form of light. The consequence of molecules› absorbing light is the creation
of transient excited states whose chemical and physical properties differ greatly
from the original molecules.

Free radicals An especially reactive atom or group of atoms that has one or more
unpaired electrons

Photoionization The phenomenon in which the absorption of electromagnetic

radiation by an atom in a gas induces the atom to emit a bound electron and thereby
become ionized.

Photodissociation Photodissociation, photolysis, or photodecomposition is a

chemical reaction in which a chemical compound is broken down by photons.
It is defined as the interaction of one or more photons with one target molecule.
Any photon with sufficient energy can affect the chemical bonds of a chemical
compound.

5.14 REFERENCES AND SUGGESTED

FURTHER READINGS
• Environmental chemistry, Stanley E. Manahan, 9th edition, Boca Raton, FL,
USA, CRC Press, 2010

154
• Environmental Chemistry, Colin Baird & Michael Cann, 5th edition WH Atmospheric
Freeman and Company, New York, 1995 Chemistry

• Principles of Environment Chemistry, James E Girard,Second Edition, Jones

and Bartlet Publishers, Sudbury MA, 2005
• Living in the Environment: Principles, Connections, and Solutions, Miller. G.T.
Brooks Cole 2012
• Introduction to Environmental Science and Technology, Gilbert M. Masters
John Wiley & Sons, USA, 2003

ANSWERS TO CHECK YOUR PROGRESS

Check Your Progress I

1. Three stages of evolution. Cosmic dust that led to formation of Earth.
Gravitational force holding the gases from escaping into outer space. Initial
atmosphere was reducing. Volcanic eruptions and Iron moving to the core . Till
stage II the nature of gases was reducing. In stage III, phoodissociation of water
vapours as well as photosynthesis led to oxygen accummulation.
2. Major gases are nitrogen and oxygen. Trace amounts of noble gases. Water
vapours and carbon dioxide. Oxides of nitrogen, ozone, ammonia, methane,
iodine.
3. Atmosphere does not get heated directly from Sun’s rays. The atmosphere
close to earth gets heated from the warm Earth. With increase in altitude,
the atmosphere gets distant from the warm Earth and temperature decreases.
Increase in temperature in any zone is due to presence of species .

Check Your Progress II

1. Atmospheric stability resists vertical mixing of air, which occurs due to
pressure difference in different altitudes. Atmospheric stability in turn depends
on the lapse rate. Accordingly, the stability varies from very stable to neutral
to unstable, depending on the decrease in temperature of the atmosphere with
altitude compared to the adiabatic lapse rate.
2. Conditons for temperature inversion. Perfect gas equation that explains the
pressure inside an insulated balloon as compared to outside, which causes
mixing or not.
(i) Instantaneous re-emission of absorbed light in case of Luminescence.
Delayed remission in case of Chemilumenescence
(ii) Change of temperature with altitude for dry ideal gas. Inclusion of heat
release due to presence of water vapour refers to wet adiabatic lapse rate

3. Layer of the Earth’s atmosphere above 50Km, which is that ionized by solar
and cosmic radiation. Atoms in this area have been stripped of one or more of
their electrons, are “ionized,” and are therefore positively charged. The ionized
electrons behave as free particles. Region that reflects and modifies radio waves

155
Chemistry of Air, used for communication and navigation. Responsible for formation of Van allen
Water and Soil belts
4. It is produced by photolysis of water at higher altitudes. HO• radical is generated
by the photolysis of nitrous acid vapour, hydrogen peroxide, ozone.
Production of HO• radical depends on the wavelength of light and availability
of the substrate
Summers will increase OH concentration. Midday time also inreases the
photolysis to increase OH radical concentration.

5. OH radical is very reactive and enters into several reactions, most commonly
H abstration occurs. Major sinks of OH radical are CO and CH4. But reacts
withH2S, SO2, NH3 and many more (Refer to fig. 8).

Check Your Progress III

1. In ground state O2 in triplet state (3O2 ), excited to singlet molecular oxygen
(1O2). Singlet oxygen may also be produced by other processes such as direct
photochemical excitation, transfer of energy from other electronically excited
molecules, ozone photolysis and high-energy oxygen producing reactions.
Upper atmosphere- oxygen atoms, O; excited oxygen molecules, O2* and ozone,
O3, excited atoms, O* Oxygen ion, O+, molrcular ion O2+.
Photoexcitation, photodissociation and other photochemical raections.

2. Eight oxides of nitrogen, three are active and abundant – N2O, NO, NO2.
Interchange and responsible for several reactions in atmosphere. Refer fig. 8

3. N2O released from microbial activity, activities in oceans The natural sources
are microbial activity of the soil in tropical regions and the major part is released
through activities in oceans. Nitrification and denitrification process in anaerobic
and aerobic conditions resp. Unreactive in troposphere. In stratosphere gets
used up by converting to NO and N2,

4. SO2 reacts with OH, O to produce H2SO4.. NO2 reacts with OH and O to produce
HNO3. Both acids react with bassic air pollutants like ammonia and lime. Acid-
base reaction of these acids affords salts of Ca and ammonium ions.

5. Fine colloidal sized solid particles or liquid droplets of diameter less than 100
µm, suspended in the air. Examples- carbonaceous material, oxides of metal,.
The composition varies with the particle’s size. Play important role in cloud
formation, electrification, fog formation. Influence visibility in the atmosphere.
act as reaction sites for heterogeneous atmospheric chemical reactions.
Particles < 0.1 µm in diameter scatter light, Rayleigh scattering, reduces
visibility (haze) and redden sunrises and sunsets.

6. Refer to table 4

156
UNIT 6 : WATER CHEMISTRY
Structure
6.0 Introduction
6.1 Objectives
6.2 Distribution of Water
6.3 Chemistry of Water-Structure and Polarity
6.4 Properties of Water
6.5 Hydrology
6.5.1 Ground Water and Water Table
6.6 Sources and Uses of Water: The Hydrological Cycle
6.7 Physical and Chemical Properties of Fresh Water and Sea Water
6.7.1 Physical Properties
6.7.2 Chemical Properties
6.7.3 Environmental Significance
6.8 Coagulation and Sedimentation
6.9 Water Quality
6.9.1 Physical Characteristics
6.9.2 Chemical Characteristics
6.9.3 Biological Characteristics
6.10 Chemical Species in Water
6.10.1 Organic Components in Water
6.10.2 Inorganic Components in Water
6.11 Distribution of Gases in Water
6.11.1 Oxygen in Water
6.11.2 Carbon Dioxide in Water
6.12 Organic Matter and Dissolved Humic Substances in Water
6.13 Let Us Sum Up
6.14 Key Words
6.15 References and Suggested Further Readings
6.16 Terminal Questions

6.0 IMPORTANCE OF WATER

WATER IS LIFE. It’s one of the most indispensable resources for all lifeforms on
Earth, playing a prime role in maintaining various ecosystems on the planet by
serving as a link between them. Water occurs in all spheres of the environment- a
vast reservoir of saline water in oceans; in rivers, lakes etc. as surface water; in
aquifers as groundwater; in polar ice caps as ice; in the atmosphere as water vapour
along with several other segments of anthroposphere.

157
Chemistry of Air, We consume several litres of freshwater daily to sustain life. As an essential
Water and Soil nutrient, water plays a key role in the human body. In fact, about 70% of the human
body is made up of water. One can survive up to multiple weeks without food,
but only a couple of days without water. Every system of the body, starting from
cells and tissues, to organs require water to function. Water serves as a medium
for the transformation of complex biomolecules forming a foundation for life
processes, ranging from respiration and digestion, to temperature regulation and
waste removal. Industries also require water at various stages of their production.
In agriculture, water is used for irrigation and livestock. Water stored in dams is
utilized in producing hydroelectric power. However, freshwater is available in
limited stock on Earth.

6.1. OBJECTIVES
After studying this unit, you will be able to
• Express the quantitative features of global water distribution,
• Discuss different stages and significance of hydrological cycle,
• Identify organic and inorganic chemical species in water,
• State the factors that decide the solubility of gases in water.

6.2 DISTRIBUTION OF WATER

The quality and quantity of available water is an important factor for the wellbeing of
life. Nearly 71% of the Earth’s surface is made up of water. In response to temperature
variations and other factors, it exists in various forms in the environment. It may be
classified as groundwater (present under earth’s surface as an aquifer) and surface
water (free-flowing water in the form of rivers, lakes etc.). As shown in figure 1,
about 97% of the total available water is present in the oceans (marine water), while
only 3% is fresh water. Ocean water is highly saline, making it unfit for drinking and
agricultural purposes. Out of remaining 3% freshwater, 79% is stored in glaciers
and polar ice caps, 20% is stored in aquifers or soil moisture, and only 1% is surface
water (primarily lakes and rivers). The water stored in glaciers and polar ice caps
as well as in aquifers or soil moisture is not available as drinking water, However,
lakes and rivers are of the main sources of potable water, constituting even less than
0.01% of the total water supply.

Several civilizations have vanished due to the shortage of water. Due to climate
change, numerous catastrophise have occurred from time to time in different parts
of the globe, may be due to droughts or due to floods on other extremes. Waterborne
diseases such as cholera and typhoid killed millions of people in the past and still
cause great misery in less developed countries. Globally, issues related to quality
and quantity of water supply are becoming more serious. These problems include
increased water use due to population growth, contamination of drinking water
by improperly discarded hazardous wastes and destruction of wildlife by water

158
pollution. An estimated 110,000 km3 of rain, snow, and ice falls annually on land Water Chemistry
surfaces and provides a mean to replenish freshwater resources.

Figure 6.1 Distribution of water

6.3 CHEMISTRY OF WATER: STRUCTURE

AND POLARITY
Water is an unusual molecule, consisting of covalently bonded two hydrogens and
an oxygen atom. On account of the difference in electronegativities of the combining
atoms, the molecule is polar in nature with an electrical dipole moment (Figure 2).
This unique attribute is responsible for many of the special characteristics of water
making it a universal solvent, with high ability to dissolve other substances. An
important property of water is its ability to form Hydrogen bonds with itself and
with other polar molecules. This property is responsible for strong attractive forces
between molecules of water, and give rise to high surface tension and capillary
forces. Hydrogen bonding plays a crucial role in retaining very small colloidal
particles in water suspension. Not only this, it also accounts for the dissolution and
transportation for several pollutants whose removal from water is often challenging.

Figure 6.2 Hydrogen bonded water molecule

159
Chemistry of Air, 6.4 THE PROPERTIES OF WATER
Water and Soil
Under natural conditions, water can exist in solid, liquid or gaseous state. A range of
unique properties determine its environmental chemical behaviour and are essential
to life.

Physical Properties of water

Water has many unique properties which are essential to life. Some of the special
characteristics of water include its polar character, tendency to form hydrogen bonds,
and high boiling point. These properties along with the respective consequences are
listed below in table 1.

At optimum temperature and pressure, all three states (solid, liquid, and vapour)
of water coexist and are in equilibrium with each other. This denotes the triple
point, wherein an infinitesimally small changes in either temperature or pressure
will cause water to be either a liquid, solid, or gas. The triple point of water is
observed at temperature and pressure of 273.16 K (0.01°C) and 611.73 pascals
(0.00603 atm), respectively. As shown in figure 3, a decrease in temperature and
an increased pressure allows water to pass to solid directly from a gaseous phase.
Water cannot exist as a liquid at pressures lower than the triple point and thus ice
converts into vapour on increasing temperature (sublimation). At pressures higher
than the triple point, increase in temperature forces ice to transform into liquid and
finally vapour state.

Table 1. Important properties of water

Property Effects and significance
Universal solvent Dissolve a large number of chemical
compounds. Allows transport of nutrients
and waste matter, making biological
processes conducive in an aqueous medium
Highest dielectric constant High solubility of ionic substances and their
ionization in solution
Melting point = 0 °C and boiling Exists as a liquid at room temperature
point = 100 °C
High surface tension Formation of water droplets allows plants
to transport water (and dissolved nutrients)
from their roots to their leaves, and the
movement of blood through vessels in the
bodies of animals
Transparent to visible and longer Colourless, thus aquatic plants survive
wavelength portion of ultraviolet beneath water because sunlight can reach
light them.

160
 Water Chemistry
Maximum density at 4 °C. Unique behaviour causes water to become
less dense when cooled down to its solid
form, ice. Ice floats and insulates deeper
water; making the existence of life even
possible at very low depths, vertical
circulation restricted in a stratified water
body.
Higher heat of evaporation (2260 Cooling effect determines the transport of
J/g)- steam contains more energy heat between the atmosphere and water
than liquid water bodies. Allow moderation of the Earth’s
climate and regulation of body temperatures
of living organisms, resulting in the cooling
effect.
Higher latent heat of fusion (-334 Temperature stabilized at its freezing point.
J/g) than any other liquid except
ammonia In high latitudes, permit heat to be stored
by melting ice during summer and returned
by freezing water to ice in winter without
affecting temperature of polar ocean water.
Higher heat capacity (4.2 J/g oC) Absorbs sun’s heat, allows moderation of
than other liquid except ammonia- the Earth’s climate and regulation of body
water can contain a large amount temperature more effectively. It is used as
of heat without undergoing much coolant.
change in temperature

Figure 6.3 Phase diagram of the triple point of water

161
Chemistry of Air, Check Your Progress – I
Water and Soil
Q.1 How does polluted water responsible to disturb ecological balance?

Q.2 Of all the water on our planet, approximately how much is fresh water, salt
water, ice, ground water? How much is easily accessible?

Q.3 Why is water a Universal Solvent ?

Q.4 Which among the following properties of water are greatly influenced by
hydrogen bonding? ( mark the correct answer amongst a, b, c and d)
1. Absorption in the visible spectrum 2. Boiling point
2. Density near the freezing point 4. Dipole moment
a) 1 and 2 b) 1,2 and 3.
c) 3 and 4. Or d) 2 and 4

6.5 HYDROLOGY
Hydrology is the branch of science dealing with the study of water on the Earth
and beneath the surface of the Earth. It encompasses the natural distribution
and movement of water, the physical and chemical properties of water, and its
relationship with the living and material components of the environment
It is classified into two broad sub-categories:
Limnology – The branch of science that deals with the characteristics of freshwater,
including their biological as well as physical and chemical properties.

Oceanography- The branch of science dealing with the study of ocean and its
physical, chemical and biological properties.

162
6.5.1 Groundwater and Water Table Water Chemistry

Groundwater plays a crucial role in geochemical phenomena such as the formation

of secondary minerals. The nature of rock formations strongly influences the quality
and mobility of groundwater resources.

The top of the groundwater (saturated) region is called the water table. Lakes and
streams are observed when the water table lies above the soil. However, the water
table may be observed at the surface of the soil giving rise to swamps. Permeability
of rocks largely impacts the flow of groundwater. For example, highly pervious
porous rock allows water to pass through pores in such rocks and later water can
also be extracted from such formation. This constitutes a permanent reservoir of
groundwater or underground lake which may be understood as Aquifer or artificial
wells (Figure 4).

Importance of groundwater can be realised by the facts that circulation of

groundwater into rivers, prevents drying up of rivers and also sustains plant life.
Earlier groundwater was regarded to be of the highest purity. However, on account
of percolation of soil and its long residing time underground, groundwater contains
natural organic matter in low concentrations and disease-causing microbes, which are
otherwise present in lakes and rivers. Increasing urbanization and industrialization
has led to groundwater pollution with continuous seeping of minerals and pollutants
down into the surface.

Figure 6.4 Water table

6.6 SOURCES AND USES OF WATER: THE

HYDROLOGICAL CYCLE
The water cycle, or hydrologic cycle, is a continuous process via which water is
purified by evaporation and recycled from the earth’s surface (including the oceans)
to the atmosphere and back to the land and oceans (Figure 5). On absorbing heat
from the sun, water from various sources evaporates as water vapour. As this moist

163
Chemistry of Air, air rises, it cools, condenses and returns to the Earth’s surface as precipitation.
Water and Soil Some precipitation penetrates the ground as groundwater, moving downward
through the incisions, forming aquifers, while the unabsorbed groundwater returns
to rivers, streams, and eventually to the oceans. This cycle repeats itself as water
evaporates from the surface of water bodies and transpiration by plants returns
the absorbed moisture into the atmosphere. Even though water regularly cycles
through the ecosystem, a fine balance between various processes like evaporation,
condensation and precipitation maintains the total water on Earth constant.

Figure 6.5 The Hydrological cycle

(Source: Int. J. Sci. Res., 9(6), 2019, 320-331. DOI: 10.29322/IJSRP.9.06.2019.p 9051)

6.7 PHYSICAL AND CHEMICAL PROPERTIES

OF FRESH WATER AND SEA WATER
As disused earlier, about 97% of the total available water on Earth is present in the
oceans (saltwater), while only 3% is freshwater. Seawater constitutes a rich source
of various commercially important chemical elements. For example, much of the
world’s magnesium and bromine is recovered from seawater. Common salt (NaCl)
is still obtained by evaporating sea water in some parts of the world. Also, sea
water after desalination can supply a limitless supply of potable water. Many such
desalination plants are operational in dry areas along the sea coast, such as Middle
East Countries.

6.7.1 Physical Properties

The waters of the Ocean are different from fresh water in physical as well as
chemical properties. The properties of seawater vary with latitude, depth, nearness
to land, and input of fresh water. About 3.5% of sea water is composed of dissolved
compounds while the remaining 96.5% is pure water. The chemical composition of
sea water gives an idea about processes such as erosion of rocks and soil, volcanic
activity, gaseous exchange with the atmosphere, metabolic and breakdown products
of organisms and rain.

164
The salt content in seawater is denoted by salinity (S). Salinity is defined as the Water Chemistry
amount of salt in grams dissolved in one kilogram of seawater. It is expressed in
parts per thousand (ppt) or practical salinity units (PSU). The average salinity of
ocean water may range from 34 to 37 ppt or 34 to 37 psu. As shown in figure 6,
the six most abundant ions of sea water, comprising about 99% of sea salts are
chloride (Cl-), sodium (Na+), sulphate (SO42-), magnesium (Mg2+), calcium (Ca2+),
and potassium (K+).

Figure 6.6. Relative proportions of dissolved salts in seawater.

Chloride makes up 55% of the salt in seawater. Inorganic carbon, boron, bromide,
strontium and fluoride constitute the other major dissolved substances in sea water.
Out of the several minor chemical constituents, inorganic phosphorus (HPO42– and
PO43–) and inorganic nitrogen (NO3–, NO2–, and NH4+) are most notable, since they
constitute essential nutrients for the growth of living organisms that inhabit the
oceans and seas.

A variety of elements essential for the growth of marine organisms, include silicate
(incorporated into the hard structural parts of some marine organisms), abundant
in the upper ocean. Dissolved silicate concentrations range between less than 1
micromole/kg on the surface to 180 micromoles/kg at depth. The concentration
of zinc ranges between approximately 0.05 nanomole/kg on the surface ocean to as
much as 6 nanomoles/kg at depth. Several other elements including cadmium, iron,
cobalt and copper show more complex behaviour. These elements get adsorbed on
the surface of the sinking particles and hence moves from the surface to a greater
depth.

Seawater also contains various dissolved atmospheric gases, mainly oxygen,

nitrogen, argon and carbon dioxide. Some other components of seawater are
dissolved organic substances, such as amino acids, organic rich particulates and
carbohydrates. These materials are mainly present in the upper 100 m of the ocean,
where the dissolved carbon is converted into organic matter via the process of
photosynthesis.

165
Chemistry of Air, Since oxygen is a reactive gas essential to life, oxygen concentrations in seawater
Water and Soil that are not in direct equilibrium with the atmosphere is quite variable. Although
oxygen is released by photosynthetic organisms at sunlit ocean depths, the
concentration of gas in near-surface water is established mainly by exchange with
the atmosphere. In the oceans, oxygen concentrations generally show minimum
values at intermediate depths and comparatively high values in deep water.

Freshwater contains less than 1% salt in comparison to almost 3% in sea water.

When it comes to chemical composition beyond simple water and salt, seawater is
very similar from place to place, whereas freshwater varies a lot depending on the
type of soil and rock the water is in contact with. Some of the distinctive qualities of
seawater are due to salt content. Due to the high salinity of sea water in comparison
to the fresh water, the former has a higher viscosity, greater density, higher boiling
point and lower freezing point than the latter. The various physical properties of
fresh water and sea water are compared in table 2.

6.7.2 Chemical properties

Water reacts with several substances to form different compounds. Some significant
reactions are as follows:

• Amphoteric nature Water is amphoteric and can act as both acid and base.
Example:
Acidic Behaviour:          H2O(l) + NH3(aq) ⇌ H3O+(aq) + NH4+(aq)
Basic Behaviour:           H2O(l) + H2S(aq) ⇌ H3O+(aq) + HS−(aq)

Redox reactions: Any electropositive elements reduce water to hydrogen molecule.

Example: 2H2O(l) + 2Na(s) → 2NaOH(aq) + H2(g)

Also, during the process of photosynthesis, water is oxidized to O2. As water can be
oxidized as well as reduced, it is very useful in redox reactions.

• Hydrolysis reaction
Since water has a high dielectric constant, it has a very strong hydrating tendency.
It dissolves many ionic and polar compounds easily. Some more reactions occur in
sea water. The total concentration of CO2 is very high in sea water, in comparison
to atmosphere. It reacts with sea water to form carbonic acid (H2CO3), bicarbonate
ions (HCO3-) and carbonate ions (CO32-). About 90% of the total organic carbon is
converted into HCO3-. During the conversion of CO2 into HCO3- and CO32-, hydrogen
ions are also liberated. However, the relatively high concentrations of both total
inorganic carbon and boron [as B(OH)3 and B(OH)4–] in seawater are sufficient
to maintain the pH of seawater between 7.4 - 8.3, thus buffering the amount of
hydrogen ion liberated. This buffering action is very important because the extent
and rate of

166
Table 2. A Comparison between physical properties of fresh water and sea Water Chemistry
water
Property Fresh water Sea water
Salinity Fresh water has very Marine water is characterised
concentration of dissolved salts, by high salt content (3.5%)
about 0.05%. that arises due to leaching
out of salt from the ocean
floor and from rivers and
streams.
Dissolved Ions Freshwater contains similar Seawater may contain
elements as present in sea water, hundreds of trace elements
but much less of everything - including metals like Pb and
fresh water is purer. Hg, large quantities of Cl-,
and smaller quantities of
Mg, S, Ca and K.
Electrical Fresh water has a lower value of Marine water has high
Conductivity electrical conductivity because electrical conductivity due
of its low salt concentration. to high salt content. for
example, sea water due to
dissolved salts conducts
electricity about 100 times
more than distilled water.
pH Fresh Water is neutral. Saltwater is more basic
because they have higher
salt content.
Density Fresh water has less density Due to dissolved salts,
than sea water. At 00C, liquid marine water is denser. A
water turns into ice, which has specific volume of salt water
a density of approximately 917 is heavier than the same
kg/m3. Fresh water at the same volume of freshwater. The
temperature has a density of density of seawater usually
nearly 1,000 kg/m3. increases with decrease in
temperature, increase in
salinity, and increasing depth
in the ocean. The density
of seawater at the surface
of the ocean varies from
1,020 -1,029 kg/m3. Highest
densities are observed with
depth due to the overlying
weight of water. In the
deepest parts of the oceans,
density of seawater can be as
high as 1,050 kg/m3.

167
Chemistry of Air,
Freezing point The freezing point of Seawater freezes at a
Water and Soil
Fresh water is 0.0°C. temperature lower than
fresh water. The freezing
temperature varies with the
salt concentrations. More is
the salt, lower is the initial
freezing temperature. At a
salinity of 35 ppt, seawater
freezes at a temperature
of -1.9°C. Hence sea
water remains liquid at
temperatures below 0°C,
and salt is used on roads and
sidewalks during the winters
to prevent freezing of water
on their surfaces.
Dissolved Oxygen dissolves in freshwater Salt water has less dissolved
Oxygen more easily than salt water, oxygen in comparison
because water can flow fast in to fresh water. Seawater
small rivers, stirring plenty of contains 10-11 ppm of
oxygen into itself. Fresh water dissolved oxygen at 0 °C.
contains 14-15 ppm of dissolved
oxygen at 00C

Temperature In smaller water bodies, which Large bodies of water, like

Fluctuation can sometimes be found in salty seas, maintain the
freshwater areas, temperature temperature more easily -
fluctuates more easily, affecting they stay cooler in summer
the aquatic life in that water and warmer in winter. The
body. temperature of the water has
more to do with the depth of
water.
Tonicity Due to osmosis, water flows Marine water is hypertonic to
from solution of higher plant and animal tissues; thus
solute concentration to a organisms tend to release
lower concentration through water to their surroundings
a semipermeable membrane. and require a regular uptake
Tonicity is important for of water to eliminate salt.
the survival of aquatic life.
Freshwater is hypotonic, thus
living organisms do not require
much water but excrete it
regularly as water is absorbed to
balance the salt concentration.

many reactions in seawater are highly pH-dependent. Carbon dioxide produced

by the combination of oxygen and organic carbon generally reduces the pH near

168
the depth of the oxygen minimum in seawater. In addition to exchange with the Water Chemistry
atmosphere and, through respiration, dissolved inorganic carbon concentrations in
seawater are also influenced by the formation and dissolution of the calcareous
shells (CaCO3) of organisms mainly in the upper ocean. It has been estimated that
dissolved Organic Carbon (DOC) near the surface of the open ocean range between
100 - 500 micromoles of C/ kg of seawater. In surface water, DOC mainly exists
as carbohydrates, amino acids, lipids and humic substance. DOC concentrations
in the deep ocean are 5 to 10 times lower than surface values, with much less
amount of carbohydrates and amino acids, as compared to the surface water. DOC
in the surface water participates actively in photochemical transformation, which
is capable of greatly altering the bioavailability of essential trace nutrients, such as,
Cu and Zn.

6.7.3 Environmental significance

A freshwater ecosystem comprises streams, wetlands, ponds, lakes, and rivers. It
provides a natural habitat for animals and plants that are unable to survive under
highly saline marine water. In contrast to freshwater ecosystem, marine ecosystem
is more diverse. It consists of salt marshes, wetlands, estuaries, mangroves, and
accommodate several different aquatic lifeforms. Some can use salt water but the
majority of higher plants and most mammals must have access to fresh water to live.
Freshwater and marine ecosystems occupying more than three-fourth of the Earth’s
surface, nurtures array of ecosystems by participating in various biogeochemical
cycles and nutrient exchange, providing natural habitat to lifeforms, and also assist
in degradation and dispersion of many environmental pollutants.

The main environmental significances of fresh and marine water life are as follows:

Habitat
Freshwater aquatic life thrives in streams, rivers and lakes, with very low saline
content. Depending on the species, fishes can survive in temperatures that range
from 5 and 24 °C. The aquatic life adapts well to changes in habitat viz, changes
in water levels, oxygen and temperature. In comparison, marine life like saltwater
fish, coral reef and seagrass bed, can only survive under high salt concentration. A
marine animal’s habitats include.

Physiology
The physiology refers to the physical conditions of the habitat in which an organism
live in. under hypotonic conditions, freshwater fish retain more salt in their bodies
than in their surrounding water. Thus, they can survive in fresh waters with very low
salt content. On the other hand, marine water fish lose water to their surroundings
via osmosis. This lifeform requires plenty of water to eliminate excess salt.

Species
Fresh and marine water are home for a variety of living species. For example,
freshwater fish include cold water or tropical varieties. Pike, trout, shiner and
goldfish are examples of cold varieties. Examples of tropical freshwater species
are pacu, golden barb, red-tailed red eye puffer, catfish, guppy and angelfish. In
comparison, marine fish are all cold-water fish, including seahorses, eels, jellyfish,

169
Chemistry of Air, clownfish, sharks, common dolphin and tuna. Fishes in Antarctica can inhabit
Water and Soil waters as cold as -2° C because of proteins in their blood that act as antifreeze. The
body structure of marine organism also varies with depth. The body structure of the
organisms that live on the surface of the water is in sharp contrast with the sleek,
elongated shape of the animals that live deep inside the sea.

Effect of human activity

Although the oceans constitute a huge reservoir, human activities have begun to
influence their composition. The addition of nutrients results in increased growth
of phytoplanktons, decreased penetration of sunlight, high level of organic
matter, and alteration of the community of bottom-dwelling organisms. Through
industrialization, the concentration of pollutants such as Pb, Hg, toxic organic
compounds, radioactive waste has increased tremendously in sea water finally
resulting in their bioaccumulation. Another recent global problem is the increase of
CO2 levels in the atmosphere. It is thought that the oceans, as a great reservoir of
carbon dioxide, will ameliorate this increase in CO2 level, but actually, it is giving
way to another problem of ocean acidification.

Check Your Progress – II

Q.1 Explain the process of hydrological cycle with suitable diagram. Also
mention the environmental significance of it.

Q.2 Differentiate between :

(i) Fresh water ecosystem and marine ecosystem
(ii) Surface water and ground water

(i)

(ii)

170
6.8 COAGULATION AND SEDIMENTATION Water Chemistry

Surface water is usually associated with dissolved and suspended particles. The
suspended matter enters the water body from land erosion, the dissolution of
minerals, decay of vegetation and domestic and industrial waste discharges. It
generally consists of suspended, dissolved organic and/or inorganic matter, as
well as several biological organisms, such as bacteria, algae or viruses. Hence,
this material has to be removed before water is put for drinking purposes, as
deteriorates water quality by reducing its clarity (causing turbidity or colour) and
carrying pathogens or toxic compounds, adsorbed on the surfaces of suspended
matter. Thus, the effluent water requires appropriate treatment to remove disease-
causing agents. The most commonly employed methods in water treatment include:
i. Coagulation and Flocculation
ii. Sedimentation
iii. Filtration
iv. Disinfection

Coagulation
The aggregation of colloidal particles is important to understand the number of
processes, like industrial processes and aquatic chemical phenomena. The colloidal
particles in minerals aggregate and separate from water is significant in the
formation of mineral deposits. Aggregation of particles is a complex phenomenon
and may be divided into two categories, namely coagulation and flocculation.

Colloidal particles are prevented from aggregation by electrostatic repulsive

forces between electrical double layers. These repulsive forces can be minimised,
allowing particles to aggregate together. For example, the addition of ions, such
as Na+ and Cl- ions, from sodium chloride forces electrically charged colloidal
particles to aggregate into larger-size particles and settle. These charged ions act by
neutralising the electrical charges on the colloidal particles and forces them to clump
together; this process is known as coagulation that removes colloidal solids from
water and accelerate the sedimentation process. Salts such as aluminium sulphate,
polyaluminium chloride (also known as PAC or liquid alum) and ferric sulphate
are frequently used as coagulant in water treatment. For example, filter alum,
Al2(SO4)3.18H2O when added to waste water, the hydrated aluminium ion which
is acidic in nature, reacts with base to form gelatinous precipitate of aluminium
hydroxide that carries suspended matter with it as it settles. Thus, the alkalinity of
water is also reduced.
[Al(H2O)6]3+(aq) + Al(OH)3(s) + 3CO2(g) + 6H2O(aq)

In some cases, colloidal particles are allowed to settle in presence of bridging

compounds, that interact with colloidal particles through chemical bonds, join
them via bridges and induce coagulation called flocculants. This process is called
flocculation. Natural and synthetic polyelectrolytes are used as flocculants. Among
the natural compounds so used are starch and cellulose derivatives, proteinaceous
materials, and gums composed of polysaccharides. Synthetic polymers, including

171
Chemistry of Air, neutral polymers and both anionic and cationic polyelectrolytes, are commonly
Water and Soil used.

Sedimentation
Wastewater can be treated by several physical processes. For example, solids
can be removed by sedimentation and filtration. Sedimentation involves physical
pre-treatment of water before application of other purification treatments such as
filtration and disinfection. It may be defined as the tendency of suspended solids
(sand, silt and clay) in the suspension of water to settle out of the suspension
under the influence of gravity. The particles that settle out from the suspension
deposit as sediment or sludge at the bottom of sedimentation tank and are removed
periodically.

Sedimentation is one of the most basic steps of purifying water. It may be used
as a preliminary step in some water treatment methods. It offers the following
advantages:
1. Effectively removes water turbidity.
2. Fewer chemicals are required for subsequent water treatment processes.
3. It makes any subsequent process easier.
4. Cost-effective

Hence, sedimentation of turbid water for household use is recommended as a

pre-treatment method that disinfects water with solar radiation, chlorine or other
chemical disinfectants. In water treatment, the process of sedimentation minimizes
the concentration of particles in effluent water before the coagulation, to reduce the
amount of coagulants required.

6.9 WATER QUALITY

Water quality refers to the physical, chemical and biological properties of water,
governing its suitability for the survival of life. It usually varies with the respective
usage of water. The characteristics of water can be classified into three broad
categories:
• Physical Characteristics: temperature, colour, odour, turbidity and solids
• Chemical Characteristics: pH, conductivity, salinity, hardness, BOD
• Biological Characteristics: counts of specific organisms and groups of
organisms

6.9.1 Physical Characteristics

Physical characteristics of water are influenced by senses of touch, sight, smell and
taste.

Temperature: Temperature measures the average kinetic energy of water molecules

in response to their thermal motion. It determines the suitability of water for various

172
aquatic life forms by controlling water quality parameters such as dissolved oxygen, Water Chemistry
rate of photosynthesis, etc.

Colour: Colour in water is primarily a concern of water quality for aesthetic

reasons. Coloured water is considered unfit for drinking purposes. It indicates the
presence of organic substances, such as algae, humic compounds, hazardous or
toxic organic materials in water. Coloured water can be treated through techniques
like coagulation, settling and filtration.

Taste and Odour: Taste and odour are perceptions to determine water quality.
Odour arises due to production of gas upon decomposition of organic matter or
other substances present in wastewater. For public supplies, the water should be
free from any odour.

Turbidity: Turbidity is a measure of the light-transmitting properties of water and

is expressed as the amount of suspended and colloidal material in mg/l or parts per
million (ppm). The factors responsible for water turbidity include human activity,
decaying plant matter, algal blooms, suspended sediments, and plant nutrients.

Solids: Total dissolved solids (TDS) refers to the inorganic salts and small amounts
of organic matter present in water. It may be defined as the residue that remains
after evaporation of water, followed by ignition and drying the residue to a constant
weight. At high temperatures, gases are released upon combustion of volatile organic
solids and the inorganic residue is left behind as inert ash. Solids are classified as
settleable, suspended and filterable solids. Settleable solids (silt and heavy organic
solids) tend to settle under gravity. Suspended solids and filterable solids are
classified on the basis of particle size and their retention rates on standard glass-
fibre filters. The solids featuring algal growths cause severe eutrophic conditions
in a water body. This leads to a reduction in light penetrating in surface waters and
thus interfere with aquatic plant life. Also, deposition of such solids on river bed
creates to septic and offensive conditions.

6.9.2 Chemical Characteristics

Upon prolonged exposures, the presence of chemicals in drinking water supply
severely affects human health and thus pose serious health concerns. The major
chemical properties of the water are discussed as follows:

pH: pH is a measure of acidity or basicity of a water sample. It may be expressed

as:
pH = -log[H+]
If [H+] increases, pH decreases and then it will be acidic.
If [H+] concentration decreases, pH increases and then it will be alkaline.

The pH scale varies from 0 (very acidic) to 14 (very alkaline). In fresh waters,
pH ranges from 4.5, for acidic waters, to above 10.0 in water featuring intensive
photosynthetic activity by algae. Th allowed pH value for public water supplies may
range between 6.6 to 8.4. It has been observed that any changes in pH may alter the

173
Chemistry of Air, concentrations of other species in water to a more toxic form. Chlorine disinfection,
Water and Soil ammonia toxicity, and heavy metal ion solubility in water are all subjective to pH
changes.

Electrical Conductivity: Conductivity is the ability to conduct an electric current

when dissolved solids ionize into constituent ions in water. Conductivity is a valuable
tool to determine hardness, alkalinity and the dissolved solids content of the water.
The conductivity is a relative term and its relation with the TDS concentration
is unique for a given water sample. The conductivity increases with increasing
concentration of TDS.

Salinity: Salinity increases with increasing concentration of dissolved salts in water.

High saline content in some saline waters may be attributed to a combination of
dissolved ions including sodium, chloride, carbonate and sulphate. The presence of
high salt content may make water unfit for domestic, agricultural or industrial use.

Alkalinity: The capacity of water to accept H+ ions is called alkalinity. Alkalinity

plays an important role in water treatment and the chemistry and biology of natural
waters. Highly alkaline water generally contains high concentrations of dissolved
solids. It reflects buffer capacity of water and serves as a reservoir for inorganic
carbon and thus helps in evaluating water’s ability to support algal growth and
other aquatic life.

Acidity: It is defined as the ability of the water to neutralize OH-. Presence of

weak acids such as H2PO4-, CO2, H2S, proteins, fatty acids, and acidic metal ions,
particularly Fe3+ are responsible for the acidic character of water body. Polluted
water contains an appreciable concentration of free mineral acid. The term free
mineral acid refers to strong acids such as H2SO4 and HCl in water.

For example, the action of hydrated metal ions with water may contribute to acidity,
[Al(H2O)6]3+ + H2O [Al(H2O)5OH]2+ + H3O+

Acidity of water is determined by titrating against a base using phenolphthalein

as an indicator to detect endpoint (pH 8.2, where both strong and weak acids are
neutralized), free mineral acid is determined by titration with a base to the methyl
orange endpoint (pH 4.3, where only strong acids are neutralized).

Hardness: The hardness of water is essentially due to the presence of Ca2+ and Mg2+
minerals (mainly bicarbonate, sulphate and chloride) present naturally in water. A
common manifestation of a hard water supply includes poor lathering of soap and
scum accompanied by the formation of the curdy precipitate. The hardness can be
of two types: temporary and permanent hardness.
2C17H33COO-Na+(aq) + Ca2+(aq) Ca(C17H33CO2)2(s) + 2Na+(aq)

Soap Hard water Precipitate

Temporary hardness is due to the presence of bicarbonates of calcium and

magnesium in water. It may be removed either by boiling the water or treating
water with lime water.

174
By heating bicarbonate salts: High temperature causes decomposition of soluble Water Chemistry
bicarbonates into insoluble calcium carbonate precipitate which can then be
removed from water using simple filtration technique.
Ca2+(aq) + 2HCO3-(aq) CaCO3(s) + CO2(g) + H2O(aq)

Treating hard water with lime water: Addition of calcium hydroxide to hard water
precipitates out calcium carbonate which can be separated by filtration.
Ca(HCO3)(aq) + Ca(OH)2(aq)→ 2CaCO3(s) + CO2(g) + H2O(aq)

Permanent Hardness arises due to the presence of sulphates and chlorides of

calcium and magnesium in water. It cannot be removed by simple boiling and hence
requires special chemical treatment for softening. For example,

Treatment with washing soda - Addition of sodium carbonate (washing soda) to hard
water converts soluble salts of calcium and magnesium into insoluble carbonate
salts, which can further be separated by simple filtration.
Na2CO3(aq) + CaCl2(aq)→ CaCO3(s) + 2NaCl(aq)

Ion-Exchange - Ion exchange resins are organic polymers containing anionic

functional groups to which the divalent cations (Ca2+) bind more strongly than
monovalent cations (Na+). Inorganic materials called zeolites which are sodium
aluminosilicate, Na3Al2SiO8 or Na2Z, (where Z = Al2SiO8) also exhibit ion-exchange
properties. Zeolites possess high reactivity towards calcium and magnesium ions
by forming insoluble calcium or magnesium zeolites. Thus, when hard water is
passed through the resin, all the cations of soluble salts of calcium and magnesium
responsible for hardness are retained with the resin and exchanged by sodium ions.
Na2Z + CaCl2 →CaZ2 + 2NaCl

Sequestration- Sequestration is an effective method of softening water without

removing Ca2+ and Mg2+ ions from the solution. The method involves the addition
of a complexing agent, which forms a stable complex with calcium and magnesium
ions and thus greatly reduces their concentrations in solution. For example, chelating
calcium ions with excess EDTA ion (Y4-), reduces the concentration of hydrated
calcium ion and prevents the precipitation of calcium carbonate. EDTA, NTA
(nitrilotriacetic acid), polyphosphate salts like sodium metaphosphate, (NaPO3)n
are the commonly used sequestering agents for water softening.
Ca2+ + Y4- →CaY2-

For streams and rivers, hardness varies between 1 to 1000 mg/L. Typical range
include 47 mg/L to 74 mg/l CaCO3 (Table 3).

Table 3. Relationship of Hardness and Classification of Natural water

Hardness as mg/L CaCO3 Classification

0 - 60 Soft
61 - 120 Moderately hard
121 - 180 Hard

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Chemistry of Air,
>180 Very hard
Water and Soil

Biochemical Oxygen Demand (BOD)- It is the amount of dissolved oxygen

required to degrade the organic matter from water by aerobic organisms at a given
temperature over a specific period of time. It widely used as an indication of the
organic quality of water and thus indicates the pollution level. It is expressed in
milligrams of oxygen consumed per litre of sample during 5 days (BOD 5) of
incubation at 20 °C. When organic matter decomposes, microorganisms feed and
oxidize the decaying material. Greater is the action of microbes, the more oxygen
will be used up giving a high measure of BOD, leaving less oxygen for aquatic life
in water.

6.9.3 Biological Characteristics

Microorganisms like bacteria, fungi, protozoa and algae are naturally present in
water and act as living catalysts playing a significant role in a vast number of
chemical processes in water and soil. Microorganism is responsible for formation
of many sediments and mineral deposits, playing a significant role in secondary
waste treatment.

Microbial contamination is one of the major concerns of water quality. Pathogenic

microbes must be eliminated before water is used for domestic purposes. Total
coliform bacteria are an entire group of bacterial species that are generally similar
to and include the species E. coli, a thermotolerant coliform many of which are
consistently present in very large numbers in the faeces of warm-blooded animals,
including man. They can survive for a considerable time in water, making them a
good indicator for the presence of other pathogenic bacteria. Untreated sewage,
badly maintained septic systems, and farm animals with access to water bodies
can cause high levels of fecal coliform bacteria to appear in and make the water
unhealthy. Thus, the detection of E. coli in drinking water supplies provides strong
evidence of fecal contamination. Hence, coliforms are considered as “indicator
organisms” in an environmental sample to assess water quality before or in place of
culturing other organisms. These bacteria help indicate measure of contamination
levels.

Check Your Progress – III

Q.1 Explain why aluminium sulphate is used as a coagulant?

176
Q.2 Discuss the application of zeolite in water treatment. Water Chemistry

Q.3 What is sedimentation ? What are the advantages of carrying out sedimentation
process prior to the water treatment ?

Q.4 Differentiate between permanent hardness and temporary hardness.

6.10 CHEMICAL SPECIES IN WATER

Water is a reservoir of a broad range of chemical species: organic and inorganic,
largely dominate the quality of water. These include soaps, detergents, pesticides,
oil, trace elements, organometallic compounds, inorganic anions.

6.10.1 Organic components in water

i. Soaps
Soaps are sodium or potassium salts of higher fatty acids such as sodium stearate,
C17H35COO-Na+ produced from the hydrolysis of fats by saponification. They are
good cleansers because of their ability to act as an emulsifying agent, lowering
surface tension of water. The organic part of the soap is an ionic carboxyl head.
Its hydrophilic nature allows soap to interact with water molecules via ion-dipole
interactions and hydrogen bonding. The hydrophobic part of the soap is a long,
non-polar hydrocarbon chain.

177
Chemistry of Air, The hydrocarbon chains are attracted to each other by dispersion forces, forming
Water and Soil cluster-like structures called micelles as shown in figure 7. In these micelles, the
carboxylate end forms a negatively charged shell or micelle with the inner lying
hydrocarbon chains. These negatively charged soap micelles repel each other
and tend to remain dispersed in water. Oil and grease are non-polar hence remain
insoluble in water.

Although soaps are good cleansers, they do have some disadvantages. Being salt of
a weak acid, soaps are converted into free acids after attack by mineral acids.

C17H35COO-Na+ (aq)+ HCl(aq) → C17H35COOH(aq) + Na+(aq) + Cl-(aq)

These free fatty acids are less soluble and hence precipitate as soap scum, making
the soap ineffective. Also, soaps form insoluble salts in hard water,

2 C17H35COO-Na+(aq) + Mg2+(aq) → [C17H35COO-]2Mg2+(s) + 2 Na+(aq)

Figure 6.7. Structure of micelle

These insoluble salts of calcium and magnesium are ineffective cleansing agents.
Hence, soaps are not regarded as potential cleansing agents for clothing, washing
etc.

ii. Detergents
Unlike soaps, synthetic detergents are excellent cleansers as they neither form
insoluble salts with hard water nor wash out of acidic waters. A molecule of
detergent consists of two major components, surfactant and builder. Surfactant
makes water “wetter” by lowering its surface tension. Owing to the amphiphilic
structural attribute consisting of both hydrophilic group such as acid anion (SO3-
, CO32-) and a hydrophobic group (alkyl chain), surfactants break the interface
between water and oil/dirt. For example,

178
 Water Chemistry

Initially, alkylbenzene sulphonate (ABS) was used as the most common surfactant
(e.g. Tetra propylene benzene sulphonate). However, due to a branched chain
structure, ABS are non-biodegradable and are replaced by a biodegradable, linear
alkyl sulphonate, LAS. The structure of LAS, α-benzenesulphonate is:

Most of the environmental problems associated with detergents are basically because
of the second component i.e. builder. Polyphosphate like sodium tripolyphosphate
Na5P3O10 is added as a builder that binds with calcium or magnesium ions. Thus,
builders act as sequestering agents which render hardness causing calcium and
magnesium ions inactive. Additionally, by imparting alkalinity to the detergent
solution, builders further improve the cleansing qualities.

However, these phosphates-based builders are non-eco-friendly and often cause

eutrophication in water bodies. An alternative to non-eco-friendly phosphates is
nitrilotriacetic acid (NTA) which significantly reduces eutrophication. However,
due to its toxic effects on aquatic life its usage is not recommended in synthetic
detergents.

iii. Insecticides
Insecticide refers to chemicals, which are used to kill insects. Even though they
are used indiscriminately in agriculture to improve productivity, they do lead to a
serious environmental problem, especially water pollution. Being water soluble,
they easily seep inside the ground and enter ground water aquifers. Contamination
of a water body by insecticides drastically changes its physical, chemical and
biological properties, making water toxic and unsuitable for uses. thereby They are
classified into the following types:

179
Chemistry of Air, 1. Chlorinated hydrocarbons
Water and Soil Chlorinated hydrocarbon-based insecticides include DDT, aldrin, heptachlor,
lindane, endrin, and toxaphene. The structures of these representative examples
are shown in figure 8. These compounds have largely been ruled out because of
their toxic nature and tendency to accumulate in food chains. For example, DDT,
dichlorodiphenyltrichloroethane or is non-biodegradable. In the presence of air/
moisture, it transforms to more toxic, DDD (Dichlorodiphenyldichloroethane).
Also, it interferes with calcium metabolism process, especially in birds.

Figure 6.8 Some organochlorine insecticides

2. Organophosphate
Organophosphates are ester derivatives of phosphoric acid. For example, paraoxon,
malathion, chloropyrifos.

Figure 6.9 Some organophosphates insecticides

Although some organophosphorus compounds are highly toxic to humans, they are
bio-degradable and usually break down in the environment and do not accumulate.
For example, malathion is hydrolysed by carboxylase enzymes to relatively
nontoxic products, as shown by the following reaction:

180
 Water Chemistry

3. Carbamates
Organic derivates of carbamic acid are known as carbamates. This group of
insecticides include carbaryl, carbofuran, and pirimicarb (Figure 10).

Figure 6.10 Carbamic acid and some insecticidal carbamates

They are widely used because of their high biodegradability than organochlorine
pesticides and low toxicities than organophosphates pesticides.

Insecticides are weakly soluble in water than in oil(fat). They easily enter and attack
the body of insect/pest. In addition, they have a high coefficient of bioaccumulation
/biomagnification, which may be expressed as:

Out of various categories of insecticides, chlorinated hydrocarbons especially DDT

has a high coefficient of bioaccumulation

iv. Herbicides
Chemicals used to kill herbs, weeds, unwanted plants, without affecting the main
crop. Initially, inorganic compounds such as NaAsO3, NaClO3, CuSO4 were used.

181
Chemistry of Air, However, owing to their toxic and non-biodegradable behaviour, they were replaced
Water and Soil by organic compounds. The organic herbicides are classified into follows:

1. Heterocyclic nitrogen compounds

These herbicides containing heterocyclic nitrogen atoms in ring structures and
are termed as triazines which used to kill grassy weeds. They attack by blocking
the stomata of unwanted herbs. Plants die due to lack of photosynthetic activity.
For example, atrazine, metribuzin used to protect corn, soybean, sugarcane when
discharged into water streams and pollute water significantly.

2. Substituted amide derivatives

This group of herbicides consist of substituted amides. For example, propanil is
used to kill grassy weeds in rice fields

3. Bipyridilium Compounds
A molecule consists of two-pyridine rings. The two important pesticidal compounds
of this category are diquat and paraquat, used to destroy crops of Marijuana

Quaternary amine groups acquire polar character, thus water soluble herbicide
readily gets into the body of the plant along with water. Herbicides are not
biodegradable; toxic; can cause diseases and even accidental death (case of
paraquat); can be carried into rivers by rainwater or be leached to groundwater
polluting these environments; some herbicides accumulate in the food chain and
thus are toxic for animals, including man.

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4. Chlorophenoxy compounds Water Chemistry
This family of compounds include 2,4-Dichlorophenoxyacetic acid (2,4-D) and
2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and are used for weed and brush
control. They are even employed as military defoliants.

v. Polychlorinated biphenyls
Polychlorinated biphenyls are present throughout the world in water, sediments,
bird tissue and fish tissues. They are characterised by high chemical, thermal and
biological stability, low vapour pressure, and high dielectric constants. As a result,
they find applications as coolant insulation fluids in transformers and capacitors,
for the impregnation of cotton and asbestos, as plasticizers and additives to epoxy
paints. An extensive usage has resulted in their accumulation in the environment.
These insoluble, dense, hydrophobic materials pose a serious concern to the water
quality as a result of their bioaccumulation in fish.

Figure 6.11 (a) General formula of polychlorinated biphenyls (left, where ‘x’ ranges from 1
to 10) and (b) a specific 5-chlorine congener

When the PCBs are discharged to the streams, the anaerobic bacteria degrade
these PCBs to mono- and dichloro-derivatives by replacing Cl by H on the more
highly chlorinated PCB molecules. The mono and dichloro-substituted PCBs are
then degraded by aerobic bacteria which oxidise the PCB molecules and cleave the
aromatic rings as shown in figure 12. Finally, the PCBs are degraded into inorganic
chlorides, carbon dioxide and water.

183
Chemistry of Air,
Water and Soil

Figure 6.12 Enzymatic process involving attack of aerobic bacteria on mono-and dichloro-
substituted PCBs

vi. Oil
Oil is a mixture of hydrocarbons containing paraffin, cycloparaffin, aromatic and
heterocyclic compounds. Presence of oil and grease in surface water is toxic to
aquatic life, especially in marine waters. It causes devastating physical effects, such
as coating animals and plants with oil and suffocating them by oxygen depletion;
form toxic products such as phenols, petroleum hydrocarbons, polyaromatic
hydrocarbons, which are inhibitory to plant and animal growth, equally, mutagenic
and carcinogenic to human beings.; destroy existing food supplies, breeding
animals, and habitats; produce rancid odours; foul shorelines, clog water treatment
plants, and form products that stay in the environment for many years. Other effects
include deadly effects on fish by coating epithelial surfaces of gills, thus inhibits
respiration and adversely impact the aesthetic value of shorelines and beaches.
Even the thinnest layer of oil is highly impermeable to sunlight and oxygen, thus
greatly hinders the photosynthesis by aquatic plants. Eventually, the concentration
of dissolved oxygen in water body decrease leading to condition, Asphixiation.

6.10.2 Inorganic components in water

i. Metal ions and Trace elements
Trace elements are those elements that occur in water at concentrations of a few
parts per million or even less. The important trace elements present in natural water
are given in table 4. Of these, many are essential at low levels but toxic at high
levels and tend to accumulate in food chains. Heavy metals are regarded as the
most harmful of the elemental pollutants in the aquatic ecosystem because of their
resistance to degradation under natural conditions. High concentrations of these

184
metals are released into the watercourses as a result of leaching from bedrocks, Water Chemistry
water drainage, runoff from riverbanks, and discharge of urban and industrial
wastewaters.

Ca2+ is the most abundant cation in water and is responsible for hardness of water. It
is essential human nutrition and a key element in the formation of teeth and bones.
Sodium and potassium commonly exist as free ions. However, these cations are
usually present in natural water in low concentrations. Other metal ions in natural
water in a concentration of 1 mg/L or higher include aluminium, strontium, iron,
manganese and zinc and non-essential metals like cadmium, mercury and lead
which are toxic even in low concentrations. These metals possess high affinity
towards sulphur, thus disrupt the functioning of sulfhydryl (containing -SH group)
enzymes, controlling the speed of crucial metabolic processes in human body. As
a result, metal bonded enzymes can no longer function normally and cause serious
health concerns. They also bond to carboxylic acid and amino groups in proteins.
The metal ions bind to cell membranes, hinder transport processes through cell
wall.

Radionuclides also are trace elements and are formed in the environment by
minerals present inside Earth’s crust, atomic collisions by cosmic rays in the Earth’s
atmosphere, as well as by human activities. They also occur naturally in rocks
and minerals and hence are frequently found in groundwater. The most common
examples of radionuclides in groundwater are uranium, radium, and radon.

The heavy metal poisoning can be treated by administration of a compound that

bonds to metal more strongly than the enzyme, such as British Anti-Lewisite
(BAL), forming a combination which is soluble and hence can be easily excreted
out of the body.

Table 4. Important Trace Elements in Natural Water

Element Maximum Sources Effects and
permissible Significance
limit (mg/L)
Beryllium 0.001 Coal, industrial waste Toxic
Boron 5.0 Coal, detergents Toxic
Chromium 0.1 Metal plating Essential as Cr(IV),
toxic as Cr(VI)
Copper 1.0 Metal plating, industrial Essential trace element,
and mining waste high concentrations
toxic to plants

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Chemistry of Air,
Fluorine (F-) 0.05 Natural geological Prevent tooth decay
Water and Soil
sources (0.05 mg/L), high
concentrations cause
fluorosis
Iodine (I-) 0.02 Natural brine, industrial Prevents goiter
waste
Iron 0.3 Industrial waste, Essential nutrient,
corrosion, acid-mine damages plumbing
drainage fixtures
Molybdenum 0.05 Industrial waste, natural Toxic
sources like legumes
Manganese 0.05 Industrial waste, acid- Toxic to plants, damage
mine drainage plumbing fixtures
Selenium 0.01 Natural sources: Essential at low
seafood, coal concentrations
and toxic at high
concentrations
Zinc 5.0 Industrial and mining Essential elements,
waste, metal plating boost immunity
Heavy metals
Lead 0.01 Industrial and mining Toxic
waste
Mercury 0.001 Volcanic eruptions, Toxic, methylmercury
fossil fuels like coal toxic to lifeforms
Cadmium 0.005 Electroplating, pigment Toxic, damages kidney
manufacturing
Arsenic 0.05 Geothermal process, Toxic, impairs
mining waste respiration

The toxicities associated with common heavy metals are discussed as follows:

a. Cadmium
Cadmium is discharged in water body through industrial and mining wastes. Acute
cadmium poisoning causes high blood pressure, kidney damage, destruction of
testicular tissue and red blood cells. Its chemical similarity with zinc ions it replaces
zinc ions in some enzymes, thus altering their stereo structures and impairing the
catalytic activity. Excess cadmium causes anaemia, hypertension, development
of tumours and bone marrow disorder. The best described incident relating to
cadmium poisoning is the Ouch-Ouch disease among residents along the Jintsu
River in Japan. It resulted in kidney failure and softening of bones accompanies by
severe pain in bones and spine.

b. Lead
Lead is released from industrial and mining sources. Leaded gasoline is the major
source of atmospheric and terrestrial lead, much of it enters the natural waters. In

186
addition, natural ore like galena (PbS) release lead to natural waters, where it exists Water Chemistry
as Pb2+ as Pb(OH)2

2Pb(s)+ O2(g) + 2H2O(l)→ 2 Pb(OH)2(s)

In excess concentrations, lead starts accumulating in body in body, displacing Ca2+

from bones resulting in weakening of bones and teeth. Being soft acid, it possesses
a strong affinity towards -SH enzyme, thus hinders with their activity. Acute lead
poisoning causes dysfunction in kidneys, reproductive system, liver and brain.

c. Mercury
Elemental mercury enters the environment through discharges from various natural
(volcanic eruptions, forest fires) and anthropogenic sources such as industrial and
mining activities, sewage waste, pharmaceutical products, amalgam dental fillings,
discarded laboratory chemicals, batteries, broken thermometers, and many more.
Elemental mercury vapour damages the nervous system when exposed at high
concentrations. Inorganic mercury compounds such as HgS, Hg(NO3)2, HgCl2 are
rapidly accumulated in kidneys and damage them. Once deposited, microorganisms
convert inorganic mercury into more toxic, organomercury compounds. These
compounds rapidly bioaccumulate collect in organisms and ‘biomagnify’ as the
concentrations increase up each level of the food chain.

The organic mercury compounds, such as. phenyl mercuric dimethyldithiocarbamate,

are used commercially as pesticides These alkyl mercury compounds are resistant
to degradation, hence are potential environmental hazard than aryl or inorganic
compounds.

Additionally, mobilization in methylated forms, (CH3)2Hg and CH3Hg in presence

of specific bacteria pose a serious concern as heavy metal pollutants in water. These
methylated forms are highly stable (t1/2 = 70 days), soluble in fat tissues and have
a high coefficient of bioaccumulation. Other toxicological effects include strong
affinity for sulfhydryl enzymes, potential to cross blood-brain and blood-placenta
barrier. A strong manifestation of mercury poisoning was realised in Minamata
disease (1953-1960) in the Minamata Bay area of Japan which had been contaminated
with mercury waste (as HgCl2) dumped from industries along the bay. More than
2000 people consumed mercury contaminated fish (total Hg concentrations > 5-20
ppm) and suffered from neurological disorders, paralysis, blindness, chromosome
breakage, and birth effects. The major damage came due to the conversion of Hg2+
to more toxic CH3Hg+ in presence of acidic industrial wastewater.

187
Chemistry of Air, The methylating agent responsible for converting inorganic mercury to
Water and Soil methylmercury compounds is an analogue of vitamin B12, methylcobalamin, which
is generated as an intermediate during the synthesis of methane by anaerobic bacteria.
Under neutral or alkaline conditions, the formation of volatile dimethylmercury,
(CH3)2Hg, is favoured.

d. Arsenic
Arsenic is released in the environment from natural sources like volcanic activities,
weathered rocks, and forest fires or human activities such as combustion of fossil
fuels, use of arsenical fungicides, herbicides and insecticides in agriculture, and
wood preservatives. Arsenic from weathered rocks and soil percolates into the
groundwater. In aquatic ecosystem, inorganic arsenic derived from rocks such
as arsenic trioxide (As2O3) and orpiment (As2S3) are dominant. In groundwaters,
arsenic exists primarily as oxy anions representing two oxidation states: As(III),
H2AsO3-(aq) and As (V), H2AsO4- (aq), where the former is more toxic.

Acute poisoning results from the ingestion of more than about 100 mg of arsenic,
while chronic exposure can cause arsenicosis, including skin lesions, blackfoot
disease, peripheral vascular disease, and cancers. Like mercury, bacterial action
also converts inorganic arsenic to more mobile and toxic organic forms, according
to the following reactions:
H3AsO4 + 2H+ + 2e- →H3AsO3 + H2O

Arsenic toxicity impairs cellular respiration by preventing ATP formation by

various mitochondrial enzymes, and uncouple oxidative phosphorylation. Arsenate,
AsO43- ion acts as phosphate analogue and replaces phosphate in Glycolysis -ATP
forming process, as shown in figure 13. The product of this reaction is 1-arseno-
3-phosphoglycerate, which is unstable and spontaneously hydrolyses to form
3-phosphoglycerate and no ATP is produced.

188
 Water Chemistry

Figure 6.13 A schematic representation of arsenic poisoning and glycolysis

ii. Inorganic species

A variety of inorganic species including metals, neutral and anionic species are
present in water under varying conditions.

a. Cyanide
Cyanide is released from natural substances, for example seeds of apples, apricots,
cherries etc. contain chemicals which metabolize to cyanide. The seeds contain
amygdalin, a glycoside unit bonded to cyanide ion. Cyanide is released in air, water,
and soil through natural processes and industrial activities.

The most toxic form of cyanide is free cyanide ion and hydrogen cyanide, HCN,
either in a gaseous or aqueous state. The presence of cyanide ion in drinking water
is a serious health concern. Once it enters the bloodstream, cyanide ion forms a
stable complex with cytochrome oxidase, an enzyme that promotes the transfer
of electrons in the mitochondria of cells during the synthesis of ATP. As a result,
cells cannot utilize the oxygen present in the bloodstream, resulting in cytotoxic
hypoxia or cellular asphyxiation. The lack of oxygen causes a shift from aerobic
to anaerobic metabolism, leading to the accumulation of lactic acid in the blood.
The combined effect of the hypoxia and lactate synthesis causes depression of the
central nervous system that may result in respiratory arrest and death.

189
Chemistry of Air, The physiological activity of cytochrome enzyme involves reversible oxidation-
Water and Soil reduction of iron species, that cycle between ferric and ferrous states.

Once Fe(II)-oxidase is being formed, it oxidises back to Fe(III)-oxidase, the electron

being released assists in conversion of ADP to ATP.

However, in presence of CN- ion, a very stable complex with trivalent iron
of cytochrome oxidase is formed. Hence, CN- ion block the active site of
ferricytochrome oxidase enzyme, thus inhibiting both cellular oxygen utilization
and ATP production.

b. Sulphate (SO42-)
Sulphate is discharged into water from naturally occurring minerals contained
in soils, aquifer rocks and sediments. Agricultural run-off, Industrial and mining
processes releasing sulphur dioxide gas (falls as acid rain), also contributes to
the sulphate content of surface waters. As such, sulphates are non-toxic to living
organisms at normal concentrations. Problems arise due to their ability to form
strong acids which change the pH. High levels of sulphate in water (above 250
ppm) may have a laxative effect, cause dehydration and are detrimental to the
human health

c. Chloride (Cl-)
Chloride enters surface water from sources like rocks containing chlorides,
agricultural run-off, waste water from industries, oil well wastes, and effluent waste
water from water treatment plants. Chlorides corrode metal, affecting the taste of
food stored in metal containers. Fish and aquatic communities cannot survive in
high level of chlorides. In humans, extracellular chloride is responsible for the
osmotic activity of body fluids and maintains electrolytic balance in the body.

d. Fluoride (F-)
Naturally, fluoride enters water through dissolution of minerals like fluorite (CaF2),
cryolite (Na3AlF6) and fluorapatite (Ca5(PO4)3F). Optimum concentration in
drinking water is vital for humans as it helps to avoid caries and prevent tooth decay.
The maximum permissible limit of fluoride in drinking water is 1.5 ppm. Excess

190
fluoride contamination in water causes dental fluorosis and skeletal fluorosis, which Water Chemistry
cause bone and joint pain.

e. Nitrite (NO2-)
Nitrite ion is present in water with a relatively narrow pE range, rarely present
in drinking water at levels over 0.1 mg/L. It is usually added as a corrosion
inhibitor in some industrial process water. high concentrations of about 1.0 mg/l
of nitrites can produce a serious condition in fish called “brown blood disease”.
In humans, nitrites react directly with haemoglobin producing methaemoglobin.
Methaemoglobin impairs oxygen carrying capacity of red blood cells and causes
methemoglobinemia or “blue baby disease”.

f. Nitrate (NO3-) and Phosphate (PO43-)

Nitrate is essential for life and is found naturally in soil and water. It is formed
during microbial decomposition of organic matter. Several nitrogenous fertilizers
are applied to crops to improve productivity. Unfortunately, nitrogen is extremely
soluble and can be leached into groundwater, from it enters the water streams. Ground
water with a concentration of nitrate greater than 10mg/l is considered as hazardous
as per EPA (Environmental Protection Agency). High nitrate concentrations in
drinking water cause prostate and gastrointestinal cancer. It is hazardous to infants
and pregnant women and causes methemoglobinemia’ or blue baby syndrome due
to deficiency of oxygen in a foetus of a pregnant woman.

Similar to nitrate, an element vital for cellular growth and reproduction, phosphorus
is one of the key elements in aquatic chemistry. The permissible limit phosphorous
in drinking water is 5 mg/L, however, beyond that limit, it causes osteoporosis and
kidney damage.

Phosphorus is discharged from point sources like sewage effluents and industrial
discharges, and non-point sources including natural decomposition of rocks and
minerals, agricultural runoff, erosion and sedimentation, animal waste, artificial
fertilisers. Phosphorus exchange with sediments pave the way for the discharge of
the element in watercourses, making phosphorous available for algae and therefore
contributes to eutrophication.

Eutrophication
It refers to the deteriorated condition of a water body with excess algal growth. The
phenomenon involves the entry of plant nutrients, typically nitrates and phosphates
which are the limiting nutrients for algal growth in many freshwater ecosystems.
According to Liebig’s Law of minima, “the growth of the plant is controlled by
a limiting nutrient, the nutrient present in minimum quantity”. With the heavy
application of fertilizers on agricultural lands, the excessive fertilisers are washed
away by rains into river or lakes and the discharge of phosphate rich detergents and
washing powders in sewage serves as a food source of phytoplankton, leading to
eutrophication. It induces algal bloom where the water becomes densely populated
with phytoplankton. A large number of floating phytoplankton produce oxygen
during day time, however, the amount of dissolved oxygen will be greatly reduced

191
Chemistry of Air, during night. This, in turn, affects photosynthesis by submerged vegetation. As
Water and Soil a result, dissolved oxygen levels decrease dramatically. Besides this, growth of
phytoplankton is followed by massive algal death due to exhaustion of nutrients.
Eventually, dead biomass starts accumulating in the bottom of the lake where it
decomposed aerobically by microorganisms and recycle nutrients carbon dioxide,
phosphorus, nitrogen, and potassium needed for plant growth. The decomposition
process further depletes the dissolved oxygen to such a level that most of aquatic
life, especially fish die of suffocation and asphyxiation. Thus, an anoxic (oxygen-
free) environment is created at the bottom of the lake, with a rise in organisms
capable of surviving under anaerobic conditions. Eutrophication not only reduces
gaseous exchange between water body and atmosphere, but is also responsible for
pungent odour and undesirable colour of the water body.

g. Ammonia(NH3))
Ammonia, soluble in water, is released naturally during biological degradation
product of nitrogenous organic waste in water. Ammonia is sometimes added to
drinking water, where it reacts with chlorine to provide residual chlorine that acts
as a disinfectant. It also enters water body through discharge of industrial effluents
containing ammonia and fertilizers. Under aqueous conditions, it is usually present
as NH4+

NH3 + H2O NH4+ + OH-

Although the ammonia is a nutrient required for life for formation of amino acids,
excess ammonia may accumulate in the living organism and cause alteration of
metabolism and is toxic to aquatic life at concentrations ranging from 0.53 to 22.8
mg/L. Toxicity increases with pH and temperature conditions. Under alkaline
conditions, fish may suffer osmoregulatory and respiratory problems.

h. Hydrogen sulphide (H2S))

Hydrogen sulphide gas is released in the environment through natural and industrial
sources. The anaerobic decay of sulphur rich organic matter releases hydrogen
sulphide in water. The objectionable rotten-eggs associated with this gas odour
makes water unfit for drinking, household use, and industrial purposes. Under
aqueous conditions, H2S is a weak diprotic acid with pKa1 of 6.99 and pKa2 of 12.92.
Thus, Sulphide ion does not exist as such in natural water and precipitates metal
sulphides on interaction with heavy metal ions, releasing H2S gas. The dissolved
gas, in turn, corrode plumbing metals, such as iron, steel, copper and brass and
exposed metal parts in washing machines and other water-using appliances and
interferes with the effectiveness of water softeners.

192
6.11 DISTRIBUTION OF GASES IN WATER Water Chemistry

Dissolved gases – oxygen for fish and carbon dioxide for photosynthetic algae are
vital for the survival of aquatic life. Gases like nitrogen are undesirable as it causes
fish death.

The solubility of gases in water can be quantitatively estimated by Henry’s Law,

which states that the solubility of a gas in a liquid is proportional to the partial
pressure of the gas in contact with the liquid.

Xg = H Pg
where:
Pg = partial pressure of gas
H = Henry’s law constant
Xg = aqueous concentration of the gas

The Henry’s law constant is a function of nature of gas or volatile organic

compounds, temperature of the liquid and constituent of the liquid (water). The
values of Henry’s constant for various gases that are slightly soluble in water at 20
°C are shown in Table 5.

Table 5. Henry’s Law Constants for gases in water at 25 °C

Gas Henry’s constant, KH (molL-1atm-1)

Oxygen (O2) 1.28 x 10-3
Nitrogen (N2) 6.48 x 10-4
Hydrogen (H2) 7.90 x 10-4
Carbon dioxide
3.38 x10-2
(CO2)
Methane (CH4) 1.34 x 10-3
Nitric oxide (NO) 2.0 x 10-4

6.11.1 Oxygen in water-

Dissolved Oxygen: It refers to the amount of gaseous oxygen (O2) dissolved in an
aqueous solution. Oxygen enters water by diffusion from the surrounding air, by
aeration (rapid movement), and as a waste product of photosynthesis of algae. The
dissolved oxygen is crucial for the survival of aquatic life. The consumption of
dissolved oxygen in degrading organic matter by microorganisms pose a serious
threat to aquatic life. Many fishes die not from the toxicity of pollutants but from a
deficiency of oxygen which is being consumed in the biodegradation of pollutants.
The hypoxic condition in water body (DO< 3mg/L) leads to reduced cell functioning
and disrupts circulatory fluid balance in an aquatic system, leading to death.

193
Chemistry of Air, It is important to understand the effect of temperature on the solubility of gases in
Water and Soil water. The solubility of oxygen in water decreases from 14.74 mg/L at 0°C to 7.03
mg/L at 35°C. At higher temperatures, the decreased solubility of oxygen is coupled
with the increased respiration rate of aquatic organisms. This eventually gives rise
to a condition wherein high oxygen demand accompanied by lower solubility of the
gas in water results in severe oxygen depletion.

6.11.2 Carbon dioxide in water

Dissolved CO2 in water is usually represented as H2CO3, a weak acid. The
equilibrium constant for the reaction
CO2(aq) + H2O H2CO3

Carbon dioxide enters water through the atmosphere and microbial decay of organic
matter. Carbon dioxide, and its ionization products, bicarbonate ion (HCO3-), and
carbonate ion (CO32-) significantly influence the chemistry of water.

Algae in water body consume dissolved CO2 in the synthesis of biomass. The
following equilibrium have a strong buffering effect upon the pH of water, for
example,

Equilibrium of dissolved CO2 with gaseous carbon dioxide in the atmosphere,

CO2 (water) → CO2 (atmosphere)

Equilibrium of CO32- ion between aquatic solution and solid carbonate minerals,
MCO3 (slightly soluble carbonate salt) →M2+ + CO32-

Carbon dioxide constitutes about 0.037% by volume of normal dry air. A reflection
of its low concentration is realised in low alkalinity of water which exists in
equilibrium with the atmosphere containing a very low level of carbon dioxide.
Nevertheless, the formation of HCO3- and CO32- greatly increases the solubility of
carbon dioxide in water. High concentrations of free carbon dioxide in water may
adversely affect respiration and gas exchange of aquatic animals and may even
cause death. The concentration of free carbon dioxide should not exceed levels of
25 mg/L in water.

A large proportion of the carbon dioxide found in water result from the bacterial
decomposition of organic matter. Even algae, consumers of CO2 in photosynthesis,
produce it via metabolic processes in the absence of light. Water seeping through
layers of decaying organic matter while permeating through the ground, it dissolves
CO2 so released by the respiration of organisms in the soil. Later, it moves through
limestone formations and dissolves calcium carbonate, contributing to the formation
of limestone caves.
CaCO3(s) + CO2(aq) + H2O → Ca2+ + 2HCO3-

194
6.12 ORGANIC MATTER AND DISSOLVED Water Chemistry

HUMIC SUBSTANCES IN WATER

Organic matter is a complex mixture of organic compounds including aliphatic
and aromatic hydrocarbons bearing functional groups such as amides, carboxyl,
hydroxyl, and ketones and others in smaller amounts. On account of the interactions
between the hydrological cycle and the biosphere and geosphere, water usually
contains organic matter. The amount and property of organic matter vary with the
origin of water. It also depends on the biogeochemical cycles of the surrounding
environment. As a carrier of metals and other hydrophobic organic chemicals, the
presence of organic matter in water is a major concern because it greatly affects
the quality of water in terms of taste and odour, colour, and bacterial growth in the
water distribution system

The natural sources like soil or anthropic sources like organic amendments (compost
or biosolids) or spillage from sanitary landfills may release the organic matter. The
organic matter may further be categorized as the abundant form, which is insoluble
under normal soil conditions and the dissolved organic matter (DOM) which enters
into water body. Dissolved organic matter (DOM) consists of soluble organic part
derived from the partial decomposition of organic matter, including soil organic
matter, plant residues, and soluble particles released by living organisms, including
bacteria, algae, and plants. Depending on the nature of the components present
in Dissolved organic matter, it can retain and/or mobilize organic and inorganic
pollutants in the environment. The common route for the organic matter in soil
and natural waters are humic substances which lend a yellowish- brown colour
to a water body. These humic substances are produced by the decomposition of
dead plant tissues, dead organisms, and excrement of living organisms by micro-
organisms. Organic matter mostly consists of humic (humic acid (HA) and fulvic
acid (FA)) and non-humic fractions, which are carbohydrates, amino acids, and
proteins

The dissolved humic substances in surface and ground waters are present in
concentrations ranging from less than 1 mg/L to greater than 100 mg/L. These
compounds are even strong complexing agents for many trace metals present
in water and also form stable soluble complexes with radionuclides. Formation
of such water-soluble complexes is of particular interest because complexation
increase concentrations of these metal ions in natural waters far greater than the
concentrations that could be expected on the basis of the solubilities of inorganic
species. The metals may be

transported in flowing groundwaters, followed by decomposition of the complex

at elevated temperatures, and all this is believed to give rise the formation of ore
deposits.

195
Chemistry of Air, Check Your Progress – IV
Water and Soil
Q.1 Though detergents can be used more effectively in hard water but their usage
is discouraged. Why ?

Q.2 Why is the use of DDT as insecticide banned ?

Q.3 Discuss briefly the toxic effects of oil pollution.

Q.4 Out of the several forms in which mercury occurs, which form is most toxic ?
Give reasons.

Q.5 Discuss the toxic effects of Arsenic in water

Q.6 Discuss toxic effects of cyanide on human health

Q.7 A large number of fish are suddenly found floating dead on a lake. There is
no evidence of any dumping of the pollutant but there is an abundant growth of
phytoplanktons. Suggest a reason for the death of the fishes.

Q.8 Write a short note on eutrophication

196
6.13 LET US SUM UP Water Chemistry

In this chapter, highlighting the importance of water, we have discussed about the
distribution and unique properties of water. Apart from various other factors, the
properties of water also depend on the salt content in it. Thus, the physical and
chemical properties of fresh water differs from those of sea water of. The presence
/ addition of chemical species, gases, and organic matter in the water not only alters
its physical properties such as colour, odour etc., but also changes its chemical and
biological characteristics.

6.14 KEY WORDS

Triple Point: The temperature and pressure at which the solid, liquid and vapour
phases of a pure substance can coexist in equilibrium

Hydrological Cycle: The sequence of conditions through which water passes from
vapor in the atmosphere through precipitation upon land or water surfaces and
ultimately back into the atmosphere as a result of evaporation and transpiration.

Coagulation: The process of a liquid becoming viscous or thickened into a coherent

mass

Sedimentation: The process of depositing or settling down of sediments

Flocculation : The process by which individual particles aggregate into clot like
mass or precipitate into small lumps. Flocculation normally occurs as a result of
a chemical reaction between the clay particles and another substance, usually salt
water.

Micelles: A cluster of molecules that is formed in certain solution, such as soap

solution

Eutrophication: Excessive richness of nutrients in a lake or other water body,

frequently due to run-off from the land, which causes a dense growth of plant life,
mainly the algae

Blue baby Syndrome : It is also known as infant methemoglobinemia, and is a

condition where a baby’s skin turns blue. This occurs due to a decreased amount
of haemoglobin in the baby’s blood. It is caused due to excessive consumption of
nitrate in drinking water

Minamata disease : It is a chronic poisoning by alkyl mercury compounds from

industrial waste, characterised by impairment of brain function such as speech,
sight and muscular coordination.

Henry’s Law : A law stating that the mass of a dissolved gas in a given volume of
solvent at equilibrium is proportional to the partial pressure of gas.

Humic Substances : an organic residue of decaying matter

Humin : A black humic substance that is insoluble in water

197
Chemistry of Air, 6.15 REFERENCES AND SUGGESTED
Water and Soil
FURTHER READINGS
1. Environmental Chemistry, Colin Baird and Micheal Cann, Fifth Edition, W H
Freemann & Company, New York, US, 1995.

2. Environmental Chemistry, Stanley E. Manahan, Seventh Edition, Boca Raton,

FL, USA, CRC Press, 2000.

3. Fundamentals of Environmental Chemistry, Third Edition , Stanley E Manahan,

CRC Press ,Taylor and Francis Group, US

4. Environmental Chemistry Fundamentals, J G Ibanez, M Esparza Hernandez, C

Serrano Doria, A Infante Fregoso, M M Singh, Springer Press ,2010

5. Introduction to Environmental Science and Technology, Gilbert M. Masters,

John Wiley & Sons, USA, 2003.

6. Chemistry for Environmental Engineering and Science, Clair N Sawyer, Perry

L McCarty and Gene F Perkin, Fifth Edition, Mc Graw Hill-Higher Education,
2003

7. Aquatic Chemistry: Chemical Equilibria and Rates in Natural Waters, Werner

Stumm, James J. Morgan, Third Edition, Wiley-Blackwell, 2010.

ANSWERS TO CHECK YOUR PROGRESS

Check Your Progress – I

Ans 1. Because of water pollution, aquatic animals and plants die and this creates
disturbance in ecological balance.

Ans 2. About 97% of the total available water is present in the oceans (marine
water), while only 3% is fresh water. Out of remaining 3% freshwater, 79% is
stored in glaciers and polar ice caps, 20% is stored in aquifers or soil moisture, and
only 1% is surface water (primarily lakes and rivers).

Ans 3. Water is capable of dissolving a variety of different substances, which is

why it is such a good solvent. And, water is called the “universal solvent” because
it dissolves more substances than any other liquid.

It is water’s chemical composition and physical attributes that make it such an

excellent solvent. Water molecules have a polar arrangement of the oxygen and
hydrogen atoms—one side (hydrogen) has a positive electrical charge and the other
side (oxygen) had a negative charge. This allows the water molecule to become
attracted to many other different types of molecules. Water can become so heavily
attracted to a different molecule, like salt (NaCl), that it can disrupt the attractive
forces that hold the sodium and chloride in the salt molecule together and, thus,
dissolve it.

Ans. 4. (b)

198
Check Your Progress – II Water Chemistry

Ans. 1 Hydrological cycle is responsible for purification and redistribution of water

on the Earth.

Ans 2 (i) Presence of excess amount of salt in sea water is responsible for
differentiating fresh water ecosystem from marine ecosystem.

(ii) Ground water is an important source but can easily become contaminated and
polluted. Pollutants such as oil, chemicals, pesticides, waste from landfills etc can
move into the ground water through soil, making the groundwater polluted.

Check Your Progress – III

Ans.1 Aluminium sulphate is frequently used as coagulant in water treatment.
Filter alum, Al2(SO4)3.18H2O when added to waste water, the hydrated aluminium
ion which is acidic in nature, reacts with base to form gelatinous precipitate of
aluminium hydroxide that carries suspended matter with it as it settles. Thus, the
alkalinity of water is also reduced.

Ans.2 It is used as ion exchanger for softening hard water.

Ans.3 Sedimentation is one of the most basic steps of purifying water. It offers
several advantages- it removes turbidity, makes the subsequent process easier, less
number of chemicals are required for subsequent treatment and is cost effective.

Ans.4 Temporary hardness is due to the presence of bicarbonates of calcium and

magnesium in water and it can be removed easily.

Permanent hardness is due to chlorides and sulphates of calcium and magnesium

and is difficult to remove.

Check Your Progress – IV

Ans.1 Most of the environmental problems associated with detergents are
basically because of an important component, builder. Polyphosphate like sodium
tripolyphosphate Na5P3O10 is added as a builder that binds with calcium or
magnesium ions. Thus, builders act as sequestering agents which render hardness
causing calcium and magnesium ions inactive.

But, these phosphates-based builders are non-eco-friendly and often cause

eutrophication in water bodies.

Ans.2 DDT is highly mobile with high coefficient of bioaccumulation. It gets

converted into even more toxic compound, DDD, on exposure to air and moisture.

Ans. 3 Presence of oil and grease causes devastating physical effects, inhibition
of plant and animal growth, produces rancid odour, clog the water treatment plant,
non-biodegradable, hinders photosynthesis, causes asphyxiation.

Ans.4 CH3Hg+ is the most toxic form, as it able to cross the blood-brain as well as
blood-placental barrier. It has a very high coefficient of bioaccumulation.

199
Chemistry of Air, Ans.5 Arsenic toxicity impairs cellular respiration by preventing ATP formation. It
Water and Soil may be further explained with equations

Ans. 6 CN- ion block the active site of ferricytochrome oxidase enzyme, thus
inhibiting both cellular oxygen utilization and ATP production. It may be further
explained with equations

Ans.7 phytoplankton are decomposed by aerobic bacteria, resulting in DO drops

Ans.8 Excessive richness of nutrients, especially nitrates and phosphates, in a lake

or other water body, which causes a dense growth of plant life, mainly the algae is
known as eutrophication.

Terminal Questions
1. Explain physical properties of water?
2. Explain various ways in which the water bodies are affected by eutrophication?
3. Explain the toxic effects of the following ions present in water.
i. Cyanide ii. Arsenic iii. Mercury

4. Describe the equilibria involving carbonic acid, bicarbonate ion and carbonate
ion?

200
UNIT 7 : SOIL CHEMISTRY
Structure
7.0 Introduction
7.1 Objectives
7.2 Origin and Nature
7.2.1 Soil Composition

7.3 Soil Formation

7.3.1 Soil Forming Process

7.4 Soil Chemical Properties

7.4.1 Soil Acidity
7.4.2 Ion Exchange Cation Exchange Capacity

7.5 Macro and Micronutrients in Soil

3.5.1 Soil Macronutrients
3.5.2 Soil Micronutrients

7.6. Soil Fertility

7.7. Let Us Sum Up
7.8. Key Words
7.9 References and Suggested Further Readings
7.10 Terminal Questions

7.0 INTRODUCTION
Derived from the Latin word ‘solum’, soil is a natural body of mineral and organic
components that form the immediate surface of the earth. Formed as result of
unabated modification of the earth’s crust by physical and biological agents, soil is
a direct interface between atmosphere, lithosphere, hydrosphere and the biosphere
that serves as a consolidated medium for further changes and developments in the
constant evolution of the earth’s surface. A complex mixture of decaying organic
matter, weathered mineral particles, water, gases and living organisms; soil is a
natural incubating medium and habitat to not only plants but all terrestrial life
forms. The physical characteristics and composition of soil largely depend upon
climate, geographical location and composition of the parent material.

The study of soil is important as it is a vital natural source for food and renewable
natural resources on which the society is largely dependent. In general, there are two
approaches towards the scientific study of soil, pedology and edaphology. While
pedology is the study of soil formation, classification and morphology; edaphology
focuses on the influence of soil on living beings. Basically, considering soil as
a natural habitat for plants, edaphology deals with study of soil productivity and
conservation.

This unit has been designed to focus on the chemistry of soil. Soil composition,
processes of soil formation and soil profile are discussed in this unit. Detailed
overview of physical and chemical properties of soil and soil fertility has also been
given.

201
Chemistry of Air, 7.1 OBJECTIVES
Water and Soil
After reading this unit, you will be able to
• understand the composition and profile of the soil,
• describe the properties of soil,
• explain the process of weathering,
• describe ion exchange properties of soil,
• explain the role of primary and secondary minerals,
• explain the role of pore spaces in soil, and
• explain various causes and the importance of soil pH.

7.2 ORIGIN AND NATURE

The formation of soil is initiated by physical and chemical weathering of rocks under
the action of various atmospheric elements such as running water, wind, changes
in temperature and living organisms. Perpetual modification of the earth’s crust by
these elements along with a myriad of complex processes involving interaction of
rocks, flora and fauna, micro-organisms and production activities of man make the
soil acquire characteristic colour, texture and pH etc.

7.2.1 Soil composition

The soil is a metre-deep layer with basic composition including mineral matter,
organic matter, water and air along with micro-organisms. Typically, soil is
constituted of 45% of inorganic or mineral matter; 5% organic matter; 25% water
and 25% air.

Inorganic or Mineral matter:

The inorganic matter of the soil is a matrix of mineral particles obtained by
decomposition and disintegration of the parent rocks by varying degrees producing
particles of various shapes and sizes (Table 3.1).

Mineral Particle Particle Size (mm)

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 Soil Chemistry
Clay < 0.002
Silt 0.02 to 0.002
Sand 0.02 to 2.0
Gravel 2.0 and above
Table 1.1: Type and size of mineral particles in soil

In this context, the term soil minerology is used which is defined by the mineral
composition of the soil. Minerals are naturally occurring compounds of inorganic
nature that have definite crystalline structures and can be classified into primary
and secondary minerals. Silicon, oxygen, aluminium, iron, calcium, potassium,
sodium and magnesium are the most common elements present in the earth’s crust
and minerals constituting these elements hence dominate the soil environment.

Primary minerals: These are the minerals that are formed under elevated
temperatures and inherit their properties from igneous and metamorphic rocks
directly without much structural alteration. The sand and the silt fraction of soil
consists mainly of primary minerals like silicates, phosphates and oxides of iron,
titanium and zircon. Silicate minerals like quartz, mica, feldspars, pyroxenes etc.
dominate the soil environment.

Secondary minerals: These are formed under low temperature reactions and
assume their characteristics from sedimentary rocks mainly. Some typical secondary
minerals present in soils include oxides, hydroxides, carbonates, sulphates and
alumino-silicates. Montmorillonite, illite, kaolinite, calcite and gypsum are a few
commonly found secondary silicate minerals in soil.

Minerals Chemical formula

Primary minerals
Silicates
Quartz SiO2
Feldspars KAlSi3O8, NaAlSi3O8
Pyroxenes MgSiO3, CaMg(Si2O6 )
Phosphates
Apatite Ca5(PO4)3 (OH, F, Cl)
Oxides
Iron Fe2O3, FeOOH
Titanium TiO2
Zirconium ZrO2
Secondary Minerals
Alumino silicates
Kaolinite Si4Al4O10(OH)8
Montmorillonite M(Al, Fe2+ , Mg)4Si8O20(OH)4
M: interlayer metal cation
Sulphates
Gypsum CaSO4.2H2O
Carbonates

203
Chemistry of Air,
Calcite CaCO3
Water and Soil
Dolomite CaMg(CO3)2
Table 3.1: Common primary and secondary soil minerals

Organic matter:
Perhaps the most important component of soil which is responsible for its
productivity is the organic matter (Fig 1.2). Though contributing only to 5% of the
total composition, organic matter is the source of nutrition for microorganisms and
provides ion-exchange sites necessary for transportation to plants and influences
the physical properties of soil. Through chemical reactions, organic matter also
contributes to the weathering of mineral matter leading to soil formation. For
example, some soil fungi produce citric acid and some other chelating organic acids
that help in release of potassium and other metal ions from silicate minerals thereby
speeding up the weathering process.

Organic matter in soil (5%)

Plant & animal residue, algae, fungi, nematodes, bacteria; nucleotides, amino sugars,
cellulose, polysaccharides, some organo-sulphur and phosphorus compounds, lignin, fats,
oils, waxes; Humus

Fig. 3.2

The most significant ingredient that forms the bulk of the soil organic matter is
humus. Humus is the residual matter produced by partial decay of plant matter
by the action of bacteria and fungi, a process called humification. The process
of humification increases the nitrogen:carbon ratio in the organic matter as the
process of decay/biodegradation results in loss of carbon as CO2, while the nitrogen
so produced is fixed by nitrogen-fixing bacteria and is incorporated in the humic
residue. A water insoluble material, humus is composed of humic substances that
are commonly classified on the basis of solubility as shown in Fig. 1.3. Humus is
very beneficial for quality of soil and the incubation of life forms supported by it
by means of the following properties:
a. Humus increases the air and water circulation within the soil
b. It provides good water holding capacity to the soil
c. It enhances the aeration of soil thereby promoting penetration of roots
d. Humus improves the physical texture of the soil by binding the soil particles
together and reducing the pore size
e. It acts as a source of food for a variety of soil organisms
f. Humus helps in maintaining and replenishing the soil nutrients

204
 Soil Chemistry
Organic bulk containing
humic substances
Extraction with strong base
followed by acidification

HUMIN HUMIC ACID FULVIC ACID

Non-extractable plant Material that Material that remains
residue precipitates from the dissolved in the
acidified extract acidified solution
Fig. 3.3

Humic substances are natural chelating agents that are capable of interacting with
metal oxides and hydroxides, metal ions and complex minerals to form metal-
organic associations of various types. This interaction or binding can occur as
chelation of metal, M with (a) a carboxyl group (b) carboxyl and phenolic groups
or (c) two carboxyl groups (Fig 1.4).

O O O

C C C O
O O M
M M O
O C
O

(a) (b) (c)

Fig. 3.4

Acid-base, complexing and sorptive properties of humic substances exert a

strong effect on the properties of soil water. They enhance the mineral breakdown
promoting nutrient availability to plants. Humin and humic acid remain insoluble
in water and act through exchange of cations or organic materials. The following
reaction shows the decomposition of microline feldspar and release of potassium
from a molecular state to an adsorbed state which is readily available for uptake by
plants.
Micelle Micelle
KAlSi3O8 + H+ HAlSi3O8 + K+
Microcline Humic acid Acid Feldspar Adsorbed K+
Feldspar

Fulvic acid (Fig 1.5) being the soluble species dissolves in water and exhibits its
effect directly. The soluble fulvic acid-metal complexes are particularly involved
in iron solubilisation and transport. The high affinity of humic and fulvic acids
towards iron and the low crystal field stabilization energies of Fe3+ and Fe2+ ions
make the minerals rich in iron more susceptible to attack by humic materials.

205
Chemistry of Air, H
O OH O
Water and Soil HO
OH H H
C
HO C C OH
O C O C O
O
H H H
H C C C C
C C C OH
H H H
OH H H C H C OH
H C C OH
OH O
H OH O

Fig. 3.5

Fulvic acids and polysachharides present in humus attract metal ions like Fe3+,
Zn2+, Mn2+ and Cu2+ from their parent minerals and form stable organo-mineral
complexes that can be taken up by plants or may take part in clay synthesis.

The humic materials i.e. humic and fulvic acids are thus capable of inducing
decomposition of soil minerals by extracting metal ions and enabling their transport
to soil environments where they can serve as nutrients. It has been observed that
it is at a pH > 6.5 that the fulvic and the humic acids are able to effectively attack
and degrade the soil minerals to form water soluble and water insoluble metal
complexes. If the metal: humic acid (or fulvic acid) ratios are high, the organo-
mineral complexes formed are water insoluble whereas a low metal: humic acid (or
fulvic acid) ratio leads to water soluble complexes.

Water soluble organic carbon

The term water soluble organic carbon refers to the entire pool of organic carbon
that is either dissolved in the interstitial pore water or is sorbed on the soil or
sediment particles. Leaching of the water soluble organic carbon becomes a source
of dissolved organic carbon (DOC) in natural waters. DOC is operationally defined
as the organic content that passes through a filter of size 0.45µm and is the major
form of carbon that gets transported with soil solution and in streams. Dissolved
organic carbon leads to hydrological transport of carbon to different pools in the
ecosystem mainly involving the transport from forest floor to the mineral soil.
However, besides contributing to the global carbon cycle, the interaction of natural
organic carbon in water with trace amount of pollutants has become a major
environmental concern. DOC has been recognized as a major carrier of persistent
organic contaminants and its potential for generating trihalomethanes and other

206
chlorinated products is often related to production of carcinogenic effects in test Soil Chemistry
organisms.

Soil water:
Water is the liquid part of the solid-liquid-gas three phase system of soil environment.
Soil water also known as the rhizic water affects the soil texture and aeration status
while playing a pivotal role as a medium of nutrient transfer from soil to plants
roots and other plant parts. The rhizic water is classified into gravitational water,
capillary water and hygroscopic water.

Fig. 3.6

The soil moisture available to plant roots is the one which is held by surface
tension and cohesive forces in the soil is termed as capillary water. Thin films of
water, hydrogen bonded to soil particles and inaccessible to plants is termed as
the hygroscopic water while gravitational water is the excess water that percolates
down to join the ground water reservoir. Soil solution is the aqueous phase that
contains a wide range of suspended and dissolved organic and mineral matter along
with some gaseous substances from various biochemical processes of the soil and
from exchange with biosphere and hydrosphere. Gaseous compounds like CO2 find
their way to the soil water by means of certain chemical reactions or as a product
of respiration of soil micro-organisms. They may enter from atmosphere by getting
dissolved in the precipitation. The CO2 concentration in the soil solution plays an
important role in determining the soil pH. Dissolved CO2 results in the formation of
carbonic acid that releases H+ ions contributing to acidity in soil:

Other factors that contribute to the acidity of soil include, industrial and urban
emissions, degradation of organic matter producing organic acids, nitrification
processes involving conversion of NH4+ ions to NO3- ions and uptake of nutritive
base cations by plants in exchange of H+ ions. Dissolution of mineral substances
contribute to the presence of mobile cations like K+, Na+, Ca+, NH+ etc. along with
chloride, nitrate and phosphate anions in the soil water. The ion concentration in the
soil solution is decided by the soil pH to a large extent. Low values of soil pH reduce
the metal adsorption capacities thereby increasing the metal concentrations in the
soil solution. Acidic conditions lead to considerable increase in the concentration
of iron and aluminium ions in the soil water.

207
Chemistry of Air, A loam (almost equal proportions of sand: clay: silt) soil with humus containing
Water and Soil approximately 60% water and close to 40% air is considered to be the best for the
growth of majority of crops.

However, soils rich in clays tend to get water logged (water-saturated). As a result,
such soils do not contain enough air required by most plant roots and hence become
detrimental for plant growth.

Soil air:
The mixture of gases occupying the pore space between the soil particles not already
occupied by soil water, in the aerated zone above the water table is termed as soil
air. Atmospheric factors like pressure, temperature and moisture control the flow of
soil air through the aerated zone. In comparison to the atmospheric composition of
air; the soil air has 1-6% less oxygen and several times more carbon dioxide owing
to the decay of organic matter that consumes O2 and releases CO2. Increased levels
of CO2 reduce the soil pH thereby promoting weathering of carbonate minerals that
in-turn leads to easy availability of mobile cations in soil water to be taken up by
plants.
[CH2O] + O2 CO2 + H2O
Organic matter

Apart from nitrogen, oxygen and carbon dioxide, trace amount of gases like
carbon monoxide (CO) and carbon disulphide (CS2) may occur in soil air due to
miscellaneous organic and mineral processes and reactions occurring in the soil
environment essentially depending on the geological composition of soil. Other
gases that may be produced within the soil include methane (CH4), hydrogen (H2)
and hydrogen sulphide (H2S).

Check your progress 1

Notes: (a) Write your answers in about 50 words

(b) Check your progress with possible answers given at the end of the unit

How does the process of humification affect the nitrogen:carbon ratio in soil organic
matter?

208
What are primary and secondary minerals present in soil. Give examples. Soil Chemistry

7.3 SOIL FORMATION

Soil forming processes

Soil formation is a complex and dynamic process involving decomposition and
disintegration of rocks due to weathering forces resulting in the formation of a
conglomerate of minerals in close association with interjacent organic matter. The
entire process of soil formation involves two stages:
(a) Weathering
(b) Pedogenesis or soil development

(a) Weathering
Natural forces like wind, running water, changes in temperature along with the
action of living organisms lead to breakdown of rocks into fine, smaller particles
that initiate the process of soil formation. These processes are collectively termed
as weathering by earth scientists. Weathering can be physical/mechanical, chemical
or caused by biological agents.

Physical/ mechanical weathering:

When the dominant forces causing the disintegration of rocks are majorly mechanical
in nature, such as erosion by the action of running water or abrasion and erosion
by wind or severe changes/ fluctuations in temperature, then one can classify the
weathering so caused to be physical or mechanical weathering. Differential thermal
expansion under severe climatic conditions; expansion due freezing of interstitial
water causing rupture; differential stress due to surface emergence of deep-seated
rocks etc. are some of the prominent agents of physical weathering. Factors like
gravity and abrasion by glacial ice further enhance the mechanical weathering.
Disintegration brought into effect by such processes cause negligible change in the
chemical or mineralogical composition of the resultant particles formed from the
parent material.

Chemical weathering-Foundation for pedogenesis:

Mechanical weathering is largely a precursor to chemical weathering as physical
disintegration of the solid of the rocky material to finer particles leads to initiation
of favourable energetics for subsequent chemical alterations. The usual chemical
processes involving acid-base reactions, hydrolysis, dissolution-precipitation and

209
Chemistry of Air, redox reactions lead to an equilibrious relation between rock-water-mineral system
Water and Soil that forms the basis of soil development or pedogenesis.

Water plays a pivotal role in attainment of such an equilibrium as it tends to hold

the weathering agents like H2SO4, HNO3, HNO2, organic acids including humic and
fulvic acids, CO2 and O2, in the solution and facilitates their transport to chemically
active sites allowing a molecular and ionic level interaction. Thus, it is evident that
chemical weathering is ineffective in desert areas due to intrinsic lack moisture.
As a result of chemical weathering the parent mineral materials are transformed
into newer mineral materials through varied processes predominantly involving the
following reactions:

1. Carbonation
It is the formation of carbonic acid by combination of carbon dioxide and water.
The carbonic acid so formed reacts with the hydroxides of calcium, magnesium and
other rock minerals leading to formation of carbonates and bicarbonates.
CO2 + H2O H2CO3
Ca(OH)2 + CO2 →CaCO3 + H2O
CaCO3 + H2O + CO2 →Ca(HCO3)2

2. Hydration
Hydration makes the mineral materials combine with water molecules thereby
increasing the volume and making the resultant material soft and prone to weathering.
CaSO4 + H2O →CaSO4.2H2O
2Fe2O3 + 3H2O →2Fe2O3.3H2O

3. Dissolution
Water soluble minerals like limestone and gypsum under the solvent action of water
increase the availability of ions in the solution form.

CaSO4.2H2O (water) →Ca2+ (aq) SO42- (aq)

4. Hydrolysis
Hydrolysis is the chemical action of water assisted by the presence of CO2. Silicates
majorly undergo weathering by means of hydrolysis as shown in the following
reactions:

Mg2SiO4 + 4CO2 + 4H2O → 2Mg2+ + 4HCO3- + H4SiO4

K2Al2Si6O16 + 2H2O + CO2 → Al2O3.2SiO2.2H2O + 4SiO2 + K2CO3

5. Oxidation
Oxidation of minerals results in the formation of their oxides. Dissolution of such
oxides in soil water weakens the rocks and assists in the weathering process. Well
aerated and drained soils promote oxidation as presence of oxygen, water and
dissolved gases under such conditions leads to dominance of oxidation reactions.
Iron, manganese and sulphur are the most commonly effected minerals by the
oxidation process.

210
 4FeO + O2 → 2Fe2O3 Soil Chemistry

4Fe2+ + 8HCO3-+ O2 → 2Fe2O3 + 8CO2 + 4H2O

2FeS2 + 2H2O + 7O2 2FeSO4 + 2H2SO4

6. Reduction
Reduction mainly occurs in the deep-seated areas of the earth’s crust that are poorly
aerated.

2Fe2O3 → 4FeO + O2

Weathering by biological agents:

Though the dominant processes of weathering may be physical or chemical, they
are always accompanied by biological agents that play an indispensable role in
the formation and evolution of soil. The intruding action of plant roots and the
physical action of rodents, worms and other organisms act as mechanical forces for
the disintegration of rock in the upper surface environment. The release of organic
acids by micro-organisms like bacteria, fungi, algae and humic matter produced
by the degradation of vegetable matter transforms the weathered mineral matter
into a dynamic system that stores energy and synthesises organic matter. This
action of organic acids primarily helps in the formation of secondary minerals like
clay and further assists in supporting miniature ecosystems and growth of plants
thus indicating the formation of embryonic soil. Ranging from simple dissolution
reactions in the acidic environment near the tips of plant roots to complex
biochemical processes, the role of chemical dimension of weathering by biological
agents is essential to the process of soil formation.

(b) Pedogenesis or soil development

The thin upper layer constituting of an unconsolidated mixture of disintegrated
mineral matter and organic matter undergoes modifications under topographic,
climatic and biological effects leading to development of distinct layers in soil that
are categorized downwards and are called the soil horizons forming the basis of
soil profile.

Factors affecting soil formation

Climatic / active factors: Rainfall, temperature, humidity are some of the climatic
factors that have a profound effect on the process of soil formation.

Topographic/ passive factors: The chemical composition, aeration status and soil
texture are mainly decided by the nature of the parent rock material and topography
which act as the passive factors in soil development.

Biospheric factors: Living organisms play a significant role in soil formation as

their mechanical and biological activities promote and modify the phsico-chemical
processes involved in soil development.

211
Chemistry of Air, SOIL PROFILE
Water and Soil
Weathering of the parent material over a period of time leads to formation of layers
of soil stacked one above the other. These horizontal layers or horizons differ in
thickness, structure, texture and composition. The structured organization of soil
layers is indicative of progressive levels of maturity of soil. A vertical section
displays of the soil components denoting its various zones from surface level to the
bed rock is called soil profile (Fig. 1.7). Generally, the soil horizons are categorized
into: organic or O horizon and mineral horizons, A, E, B and C.

O-ZONE

A-ZONE

E-ZONE

B-ZONE

C-ZONE

BED ROCK

Fig. 3.7: Soil Profile

O-Horizon: It is the uppermost horizon of the soil profile also known a the litter
zone. This layer is generally found in forests and is not present in desert or cultivated
fields.

A-Horizon: The A Horizon also called the top soil is several inches thick and
contains most of the soil organic matter ranging from undecomposed to completely
decomposed humus. The plant roots are also present in this layer which has the
maximum biological activity and is essential for plant productivity.

E-Horizon: This is the layer of elution of clay and oxides of iron and aluminium by
weathering or leaching leaving a concentration of sand and silt particles

B-Horizon: This layer forms the subsoil or the zone of accumulation. The material
dissolved from horizon A makes its way to this zone and gets re-deposited.

212
The water percolating downwards from horizon A is rich in organic acids and Soil Chemistry
complexing agents and thus leaches out minerals in the form of metal oxides which
get precipitated in this region along with organic matter and colloidal material
through the process of eluviation which thereby enriches the B zone of soil.

C-Horizon: This soil zone lacks organic matter and is largely composed of the
weathered material from the parent rock. Beneath the C horizon is the bed rock,
parent material and even older sediments from past pedological cycles.

Check your progress 2

Notes: (a) Write your answers in about 50 words

(b) Check your progress with possible answers given at the end of the unit

1) What are the two main stages of soil formation?

2) Explain with the help of reactions, how water assists the process of chemical
weathering.

7.4 SOIL CHEMICAL PROPERTIES

Soils exhibit characteristic chemical properties depending upon their chemical
composition and also the degree of agricultural exploitation. These soil features
act as relevant indicators of its origin and plant nutrition potential and hence the
land use value. Soil acidity (pH), ion exchange and cation adsorption capacities are
some of the important factors that decide the nature of soil environment.

7.4.1 Soil acidity (pH)

The acidity of soil is directly related to the soil mineralogy and organic content of
the soil. Soil pH also has a direct effect on the solubility of metal ions and hence
their availability and chelation capacity. Acidity of soil (pH) is usually measured
in a dilute (0.01M) solution of calcium chloride or in a 1:2.5 (weight to volume)
suspension of soil in water. The acidic soils are generally rich in the mineral ions of

213
Chemistry of Air, calcium and magnesium as their precipitation as carbonates increases the buffering
Water and Soil capacity of the solution.
Ca2+ + CO2 + H2O CaCO3 + 2H+

Aluminium ions (Al3+) also play an important role in soil buffering as exhibited in
the following hydrolysis reaction generally prevalent in humid and clay rich soils.
Al(OH)2+ + 2H2O Al(OH)3 + 2H+

Depending upon the availability and saturation of ions like Mg2+, Na+, K+ and
Ca2+, the soil pH may keep changing over time. The concentration of these base
cations is largely affected by atmospheric agents like weathering, precipitation and
agricultural exploitation by use of fertilizers which in turn leads to fluctuations in
the soil pH value. Some of the factors that contribute to lowering of soil pH are
listed below:
a. Production of organic acids by soil microorganisms
b. High organic matter content in soil
c. Loss of basic cations through plant harvest and leaching
d. Addition of acids in the soil environment by atmospheric agents
e. Greater uptake of cations than anions by plants
f. Production of mineral acids in soil:

Pyrite (FeS2) containing minerals present in soil are prone to aerial oxidation
leading to the formation of acid-sulphate soils called ‘cat-clays’ that may have pH
as low as 3.0.

FeS2 + 7.5O2 + H2O Fe2+ + 2H+ + 2SO42-

Potential acid-sulphate formation can be tested in the soils by performing a peroxide

test, which involves oxidizing the FeS2 in soil with 30% H2O2 followed by testing for
acidity and sulphate. A pH value lower than 3.0 and appreciable levels of sulphate
indicate the potential to form acid-sulphate soils.

Addition of acid forming chemicals by means of inorganic fertilizers:

2NH4+ +3O2 2NH2- + 4H+ + 2H2O

Soils of humid regions generally associate with low values of pH as the content of
mineral acids and organic acids remains subject to recharge by rainfall. The attack
of these acids on minerals further adds to the acidity of the soil. Whereas under
arid conditions, such as in deserts, the soil tends to have higher values of pH due
to dominance of minerals that are salts of weak acids and strong bases. Further, the
addition of carbonates by atmospheric agents, hydrolysis of exchangeable sodium
ions and greater uptake of anions by plants also contribute to soil alkalinity.

214
7.4.2 Ion exchange in soil and cation exchange capacity Soil Chemistry

One of the most important chemical functions of the soil is exchange of cations
and the ability to do so is defined in terms of cation exchange capacity (CEC).
The CEC is a measure of the potential of cation adsorption and also a measure of
surface negative charge. The cation exchange capacity of soils is measured by the
cation yield of the soil through extraction with a solution of ammonium acetate and
is expressed in milli equivalents of monovalent ion per 100g of soil.

Exchangeable cations are those that are held on the surface of clay and organic
particles or clay-humus complex and also between the layers of clay minerals, thus
cation exchange is prevalent at both the mineral and the organic portions of the soil.
The clay minerals are able to exchange cations due to the availability of negatively
charged sites on the mineral surface that are formed when atoms of lower oxidation
number (Mg2+) are exchanged for the ones with higher oxidation number (Al3+). The
surplus negative charge enables the mineral to act as a cation exchanger. Presence
of carboxylic and phenolic groups in the organic component of the soil make it
possible for it to exchange cations. The value of CEC, therefore has a dependence
upon the organic and clay content of the soil apart from clay mineralogy and soil
acidity (pH).

There is preferential take up of certain cations by the cation exchange sites and one of
the controlling factors for adsorption and replacement of ions is the valency. Cations
possessing high valency have a high energy of adsorption and are preferentially
adsorbed over cations with a lower valency. This fact also explains the relative
concentration of the ions in soil composition in accordance with the given sequence.
These cations will be less readily replaced and hence the order. Further, the cations
lying close to negatively charged exchange sites are more strongly attracted thereby
leading to preferential adsorption of cations with a smaller radius of hydration.

Ca2+>Mg2+>K+>Na+

Given the exchange reaction for the ions A+ and B+ is:

[Soil]A+ + B+ [Soil]B+ + A+

At chemical equilibrium we have:

KAB = [SB][A ]
+

+
[SA][B ]

Where SA and SB represent ionic fraction of A+ and B+ bound to the soil; [A+] and
[B+] represent the ions present in the surrounding solution and KAB is the exchange
constant for the reaction which expresses the relative tendency of soil to retain A+
and B+. Then for a soil with all exchange sites occupied by A+ , the value of SA is 1.0
while with half of the sites occupied by A+ , the value of SA will be 0.5 and so on.

Cation exchange in soil is directly related to increase in the soil acidity. This can
be explained by the fact that elements like K, Mg, Ca and other essential metals

215
Chemistry of Air, are made available to the plants through cation exchange. During this process,
Water and Soil hydrogen ions are exchanged for the uptake of metal ions by the plant roots, thereby
contributing to decrease in soil pH value. However, soil tends to resist the change
in pH and the buffering capacity depends on the type of soil.

{Soil}Mg2+ + 2CO2 + 2H2O →{Soil}(H+)2 + Mg2+(root) + 2HCO3-

Like CEC, the anion exchange capacity (AEC) of soils represents the total amount
of exchangeable anions that can be adsorbed by the soil. While cation exchange
process dominates the soil environment, exchange of anions is rare owing to
the fact that as acid radicals, the anions in the presence of hydrogen lead to the
dissociation of adsorbent surfaces like the clay minerals. However tropical soils
have been observed to possess appreciable AEC in comparison to temperate soils.

The oxide surface in the mineral portion of the soil may act as a seat for anion
exchange. At low values of pH the metal oxide surface acquires a net positive
charge thereby holding anions like halides by electrostatic attraction (Fig 1.8).
-
O H+X

M OH2

Fig. 1.8

At higher values of pH, the metal surface loses H+ ions from water molecules bound
to its surface thereby forming OH ions and hence a net negative charge on the
surface (Fig. 1.9 a). Under such circumstance anion exchange between OH- on
the metal surface and anions like HPO42- in the surrounding soil water becomes
possible (Fig. 1.9 b).

O
-
M OH

Fig. 1.9 a

O O -
+ OH
+ HPO42-
- -
M OH M OPO3H2

Fig. 1.9 b

Check your progress 3

Notes: (a) Write your answers in about 50 words

(b) Check your progress with possible answers given at the end of the unit

216
How is soil acidity measured? What term is used to describe the ability of soil to Soil Chemistry
exchange cations?

What are cat-clays and how can they be tested? Give the reactions involved.

7.5 MACRO AND MICRONUTRIENTS IN SOIL

7.5.1 Soil Macronutrients

Plants thrive on the nutrients provided by the soil and hence supporting plant
growth by supplying various nutrients is one of the primary functions of the
soil. Carbon, oxygen, hydrogen, nitrogen, phosphorus, potassium, magnesium,
calcium and sulfur are considered to be essential plant macronutrients. Among the
macronutrients essential for the growth of plants, carbon, hydrogen and oxygen are
taken up from the atmosphere while nitrogen, phosphorus, potassium and others
are taken up directly from soil. These nutrients are commonly added in the form of
fertilizers to make up their deficiency in the soil.

Nitrogen
Nitrogen is a not a substantial product of mineral weathering and is rather sourced
through the organic component of the soil i.e. the biodegradation of dead plants,
animals and soil microorganism activities. The amino nitrogen so obtained is
hydrolysed to the NH4+ form which is further oxidised by soil bacteria to the nitrate
form (NO3-).
RNH2 + H2O →R-OH + NH3 (NH4+)
NH3 + 2O2 →H+ + NO3- + H2O

However, the in-situ production of these utilizable forms of nitrogen does not meet
the requirement of nitrogen demand. Also, the nitrogen supplements added in the
form of fertilizers and through rain are often leached away. The organic nitrogen
bound to soil humus serves as a reserve for uptake by plants and plays an important
role in maintaining the soil fertility as the rate of nitrogen release through the
gradual decay process parallels the plant growth rate thus providing a sustainable

217
Chemistry of Air, nutrient source. Most plants thrive on NO3- form of nitrogen while few like rice take
Water and Soil up ammonium.

Nitrogen forms an essential component of proteins and living matter and crop
produced on nitrogen rich soils are therefore significantly richer in protein and
more nutritious. An important source contributing to the soil nitrogen content is
atmospheric nitrogen fixation by leguminous plants like clover and soyabean that
contain the nitrogen fixing bacteria of the Rhizobium species present in their root
nodules. Sustainable nitrogen content and soil fertility can be maintained by crop
rotation between legumes and nitrogen consuming plants. Figure 1.10 gives a
comprehensive outlay for the sources and sinks of nitrogen.

Fig 3.10

Phosphorus
Phosphorus as phosphates may get incorporated in the soil environment as a
product of mineral weathering. Phosphorus is taken up by the plants in the form
of inorganic orthophosphate species like H2PO4- and HPO42- that are available
in the soil at a near neutral pH. At lower pH values the orthophosphate ions get
precipitated by species of Fe3+ and Al3+ while under alkaline conditions, they may
react with calcium carbonate to form the insoluble hydroxyapatite form.
3HPO42- + 5CaCO3 + 2H2O Ca5(PO4)3(OH) + 5HCO3- + OH-

Potassium
Potassium is available to the plants in the form of exchangeable K+ held by clay
minerals. Potassium is one of the most abundant elements of the earth’s crust (2.6%)
and is important for activation of certain enzymes and carbohydrate transformations
that are essential to the growth of plants apart from maintaining water balance
in plants. Growing plants consume significant levels of potassium and potassium
deficiency adversely affects crop yields. Soils heavily fertilized with other nutrients

218
face enhanced removal of potassium making it a limiting nutrient. For example, Soil Chemistry
addition of nitrogen fertilizers to soil in turn increases potassium removal.

Calcium
Normally soils are rich in calcium but calcium deficiency may arise due to plant
uptake and leaching by carbonic acid. Also, presence of high levels of potassium,
magnesium and sodium sometimes lead to calcium deficiency owing to the
competition among ions for uptake by plants. Treatment of acidic soils by liming or
application of calcium carbonate makes up for the calcium deficiency if any.

{Soil}(H+)2 + CaCO3 + 2H2O {Soil}Ca2+ + H2O + CO2

Magnesium
Most of the magnesium in the earth’s crust is strongly bound in the form of
minerals, while the exchangeable Mg2+ ions on the exchange sites of organic or clay
component of the soil is available for uptake by plants. Excessive levels of sodium
or potassium in soil and high calcium/magnesium ratio may result in magnesium
deficiency.

Sulfur
Sulfur is a constituent element of some essential amino acids like thiamine and
biotin and is taken up by the plants in the form of sulphate ions (SO42-) that are
usually present as soluble salts in soil water or as immobilized sulphate minerals
that are insoluble. Sulfur deficient soils do not support healthy plant growth and
deficiency can be made up in the form of sulfur containing fertilizers. Sulfur present
in the form of FeS2 in soil may react with acid in acid-sulphate soils to release H2S
that is hazardous to plants and soil microorganisms.

7.5.2 Soil Micronutrients

These elements are required by the plants in trace amounts and may prove to be toxic
at elevated concentrations. Chlorine, iron, manganese, boron, copper, molybdenum
and zinc are recognized as essential plant micronutrients. These mineral elements
enter the soil environment mainly through weathering and are important for
functioning of some essential enzymes. Iron, chlorine, manganese and zinc may be
involved in the photosynthesis.

7.6 SOIL FERTILITY

Soil fertility is defined as the ability of soil to provide all the essential nutrients
in utilizable form for uptake by plants in a balanced proportion. It is recognized
as a combined effect of the three interacting components, physical, chemical and
biological characteristics of the soil. It is different from soil productivity in the
sense that fertility indicates the status of available plant nutrients in soil whereas
productivity is a result of various factors that affect crop production including
fertility.

219
Chemistry of Air, A fertile soil would contain all the macro nutrients required for basic plant nutrition
Water and Soil such as N, P, K along with the nutrients required in minor quantities. A fertile soil
is also characterized by a near neutral pH with the presence of sufficient amount
of soil organic matter that helps improve soil structure for optimal retention of
moisture and nutrient elements. However, not all soils have optimum conditions for
plant growth and all essential nutrients in adequate quantities. Soil fertility and crop
production can thus be improved by using fertilizers.

Common soil fertilizers contain nitrogen, phosphorus and potassium as major

components, while magnesium, sulphate and a few micro nutrients may also be
added. These fertilizers are designated by numbers that represent the percentage
composition of the fertilizer. For example, a fertilizer numbered as 6-8-12 is
indicative of a composition of N-6%, P as P2O5-8% and K as K2O-12%. Organic
fertilizers like manure usually correspond to a 0.5-0.24-0.5 composition and need
to undergo biodegradation to release the nutrients in form of nitrates, phosphates
and exchangeable potassium that can be readily assimilated by plants.

Check your progress 4

Notes: (a) Write your answers in about 50 words

(b) Check your progress with possible answers given at the end of the unit

What nutrients are added to soil in the form of fertilizers to make up their deficiency?

What does a fertilizer numbered as 5-10-10 indicate?

7.7 LET US SUM UP

In this unit we have elaborated upon the importance of soil, its nature, chemical
properties and composition along with various processes that are involved in the
formation of soil. The study of soil is based on two approaches, pedology that deals
with studying soil as a natural body while edaphology deals with the study of soil
properties with respect to plant production. The formation of soil basically embodies
two stages. The genesis is initiated by weathering of rocks by physical, chemical

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and biological agents while the second stage is pedogenesis which involves an Soil Chemistry
interplay of several factors and complex processes before a consolidated medium
for proliferation of life can be formed. Thus, soil formation is a continued process
witnessing changes, developments and evolution. As a result of constant evolution,
the soil develops a profile in the form of various layers stacked over one another,
differing in structure, texture, thickness and composition. Miner matter is the major
constituent of soil (45%), while organic matter which majorly influences productivity
of soil, stands at 5%. The rest 50% is air and water in equal ratios. Depending upon
the chemical composition, soil exhibits typical chemical properties. The nature of
soil environment and hence its plant nutrition potential is decided by some key
properties like acidity, ion exchange and cation adsorption capacities. Soil supports
plant growth and providing various plant nutrients is the primary function of soil
thereby making soil fertility an important aspect of studying soil.

7.8 KEY WORDS

Humus : Humus constitutes the bulk of the soil organic
matter. It is produced by the process of humification
which is partial decay of plant matter by the action
of bacteria and fungi.

Rhizic water : Soil water is also called rhizic water. It is the liquid
part of the soil environment and plays and important
role in transfer of nutrients from soil to plants

Weathering : The processes that collectively lead to breakdown

of rocks into smaller fine particles by the action of
natural forces like wind, water, temperature change
etc. are called weathering. It forms the basis of soil
formation

Pedogenesis : Development of soil and its different layers under

the influence of various topographic, climatic and
biological effects

Soil profile : Sectional display of soil components in a vertical

fashion denoting various zones from surface to the
bed rock.

Cation exchange capacity : A measure of the total capacity of soil to hold

exchangeable cations. It is a useful indicator of
soil fertility. Expressed in milli equivalents of
monovalent ion per 100g of soil

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Chemistry of Air, 7.9 REFERENCES AND SUGGESTED
Water and Soil
FURTHER READINGS
1. Manahan, S.E. (2010). Environmental Chemistry. CRC Press. Taylor & Francis
Group.
2. Mirsal, I.A. (2008). Soil Pollution: Origin, monitoring and Remediation.
Springer.
3. Wright, R.T., Boorse, D.F. (2017). Environmental Science: Toward a Sustainable
Future. Pearson
4. Bohn, H.L., O’Connor, G.A., Mc Neal, B.L. (2001). Soil Chemistry. John Wiley
& Sons, Inc.

ANSWERS TO CHECK YOUR PROGRESS

Check Your Progress 1

The nitrogen:carbon ratio in the organic matter increases by the process of
humification. This is so because humification involves decay or biodegradation of
plant material during which carbon is evolved and lost as CO2, while the nitrogen
so produced is fixed by nitrogen-fixing bacteria and is incorporated in the humic
residue.

Primary minerals: These are the minerals that are formed under elevated temperatures
and inherit their properties from igneous and metamorphic rocks directly without
much structural alteration. Examples: Quartz, feldspars, pyroxenes

Secondary minerals: These minerals are formed under low temperature reactions
and assume their characteristics mainly from sedimentary rocks. Examples:
kaolinite, calcite, gypsum.

Check Your progress 2

(a) Weathering (b) Pedogenesis or soil development

One means by which chemical weathering comes into effect is by the chemical
action of water which can happen in the following ways:

a. Hydration
Hydration makes the mineral materials combine with water molecules thereby
increasing the volume and making the resultant material soft and prone to weathering.
CaSO4 + H2O CaSO4.2H2O
2Fe2O3 + 3H2O 2Fe2O3.3H2O

b. Dissolution
Water soluble minerals like limestone and gypsum under the solvent action of water
increase the availability of ions in the solution form.
CaSO4.2H2O (water) Ca2+ (aq) SO42- (aq)

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c. Hydrolysis Soil Chemistry
Hydrolysis is the chemical action of water assisted by the presence of CO2. Silicates
majorly undergo weathering by means of hydrolysis as shown in the following
reactions:
Mg2SiO4 + 4CO2 + 4H2O → 2Mg2+ + 4HCO3- + H4SiO4
K2Al2Si6O16 + 2H2O + CO2 → Al2O3.2SiO2.2H2O + 4SiO2 + K2CO3

Check Your Progress 3

1) Acidity of soil (pH) is usually measured in a dilute (0.01M) solution of
calcium chloride or in a 1:2.5 (weight to volume) suspension of soil in water.
CEC: Cation Exchange Capacity

2) Pyrite (FeS2) containing minerals present in soil are prone to aerial oxidation
leading to the formation of acid-sulphate soils called ‘cat-clays’ that may
have pH as low as 3.0.
FeS2 + 7.5O2 + H2O Fe2+ + 2H+ + 2SO42-

Potential acid-sulphate formation can be tested in the soils by performing a peroxide

test, which involves oxidizing the FeS2 in soil with 30% H2O2 followed by testing for
acidity and sulphate. A pH value lower than 3.0 and appreciable levels of sulphate
indicate the potential to form acid-sulphate soils.
+ 15/ H + 2SO 2- + 7H
FeS2 2 O
2 2
Fe3+ + H+ 4 2O

Check Your Progress 4

1) Nitrogen, Phosphorus and Potassium
2) A fertilizer numbered as 5-10-10 is indicative of a composition of N-5%, P
as P2O5-10% and K as K2O-10%.

7.10 TERMINAL QUESTIONS

1. List out the main weathering agents involved in chemical process of weathering?
2. Distinguish between micro and macronutrients and give suitable examples
each?
3. Describe the soil horizons and explain their importance in determining the soil
properties?
4. Describe ion exchange process in the soil?

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